Coarsening phenomena of metal nanoparticles and the influence of the support pre-treatment: Pt/TiO2(110)

One of the technologically most important requirements for the application of oxide-supported metal nanoparticles (NPs) in the fields of molecular electronics, plasmonics, and catalysis is the achievement of thermally stable systems. For this purpose, a thorough understanding of the different pathways underlying thermally-driven coarsening phenomena, and the effect of the nanoparticle synthesis method, support morphology, and degree of support reduction on NP sintering is needed. In this study, the sintering of supported metal NPs has been monitored via scanning tunneling microscopy combined with simulations following the Ostwald ripening and diffusion-coalescence models. Modifications were introduced to the diffusion-coalescence model to incorporate the correct temperature dependence and energetics. Such methods were applied to describe coarsening phenomena of physical-vapor deposited (PVD) and micellar Pt NPs supported on TiO₂(110). The TiO₂(110) substrates were exposed to different pre-treatments, leading to reduced, oxidized and polymer-modified TiO₂ surfaces. Such pre-treatments were found to affect the coarsening behavior of the NPs.No coarsening was observed for the micellar Pt NPs, maintaining their as-prepared size of ~ 3 nm after annealing in UHV at 1060 °C. Regardless of the initial substrate pre-treatment, the average size of the PVD-grown NPs was found to increase after identical thermal cycles, namely, from 0.5 ± 0.2 nm to 1.0 ± 0.3 nm for pristine TiO₂, and from 0.8 ± 0.3 nm to 1.3 ± 0.6 nm for polymer-coated TiO₂ after identical thermal treatments. Although no direct real-time in situ microscopic evidence is available to determine the dominant coarsening mechanism of the PVD NPs unequivocally, our simulations following the diffusion-coalescence coarsening route were in significantly better agreement with the experimental data as compared to those based on the Ostwald-ripening model. The enhanced thermal stability of the micellar NPs as compared to the PVD clusters might be related to their initial larger NP size, narrower size distribution, and larger interparticle distances.     

Gateaux differentiability in Orlicz–Lorentz spaces and applications

Let Λ_w,? be the Orlicz–Lorentz space. We study Gateaux differentiability of the functional ψ_w,? (f) = ? (f *)w and of the Luxemburg norm. More precisely, we obtain the one‐sided Gateaux derivatives in both cases and we characterize those points where the Gateaux derivative of the norm exists. We give a characterization of best ψ_w,? ‐approximants from convex closed subsets and we establish a relation between best ψ_w,? ‐approximants and best approximants from a convex set. A characterization of best constant ψ_w,? ‐approximants and the algorithm to construct the best constant for maximum and minimum ψ_w,? ‐pproximants are given. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nonlinear Chebyshev approximation to set-valued functions

In this paper, we give a characterization of best Chebyshev approximation to set-valued functions from a family of continuous functions with the weak betweeness property. As a consequence, we obtain a characterization of Kolmogorov type for best simultaneous approximation to an infinity set of functions. We introduce the concept of a set-sun and give a characterization of it. In addition, we prove a property of Amir–Ziegler type for a family of real functions and we get a characterization of best simultaneous approximation to two functions     

Best Local Approximation in Orlicz Spaces

We get results in Orlicz spaces L ^φ about best local approximation on non-balanced neighborhoods when φ satisfies a certain asymptotic condition. This fact generalizes known previous results in L ^p spaces.     

Evolution of the structure and chemical state of Pd nanoparticles during the in situ catalytic reduction of NO with H2

An in-depth understanding of the fundamental structure of catalysts during operation is indispensable for tailoring future efficient and selective catalysts. We report the evolution of the structure and oxidation state of ZrO(2)-supported Pd nanocatalysts (～5 nm) during the in situ reduction of NO with H(2) using X-ray absorption fine-structure spectroscopy and X-ray photoelectron spectroscopy. Prior to the onset of the reaction (≤120 °C), a NO-induced redispersion of our initial metallic Pd nanoparticles over the ZrO(2) support was observed, and Pd(δ+) species were detected. This process parallels the high production of N(2)O observed at the onset of the reaction (>120 °C), while at higher temperatures (≥150 °C) the selectivity shifts mainly toward N(2) (～80%). Concomitant with the onset of N(2) production, the Pd atoms aggregate again into large (6.5 nm) metallic Pd nanoparticles, which were found to constitute the active phase for the H(2)-reduction of NO. Throughout the entire reaction cycle, the formation and stabilization of PdO(x) was not detected. Our results highlight the importance of in situ reactivity studies to unravel the microscopic processes governing catalytic reactivity.     

Structure, chemical composition, and reactivity correlations during the in situ oxidation of 2-propanol

Unraveling the complex interaction between catalysts and reactants under operando conditions is a key step toward gaining fundamental insight in catalysis. We report the evolution of the structure and chemical composition of size-selected micellar Pt nanoparticles (～1 nm) supported on nanocrystalline γ-Al(2)O(3) during the catalytic oxidation of 2-propanol using X-ray absorption fine-structure spectroscopy. Platinum oxides were found to be the active species for the partial oxidation of 2-propanol (<140 °C), while the complete oxidation (>140 °C) is initially catalyzed by oxygen-covered metallic Pt nanoparticles, which were found to regrow a thin surface oxide layer above 200 °C. The intermediate reaction regime, where the partial and complete oxidation pathways coexist, is characterized by the decomposition of the Pt oxide species due to the production of reducing intermediates and the blocking of O(2) adsorption sites on the nanoparticle surface. The high catalytic activity and low onset reaction temperature displayed by our small Pt particles for the oxidation of 2-propanol is attributed to the large amount of edge and corner sites available, which facilitate the formation of reactive surface oxides. Our findings highlight the decisive role of the nanoparticle structure and chemical state in oxidation catalytic reactions.