Enhanced thermal stability and nanoparticle-mediated surface patterning: Pt/TiO2(110)

This letter reports (i) the enhanced thermal stability (up to 1060 degrees C) against coarsening and/or desorption of self-assembled Pt nanoparticles synthesized by inverse micelle encapsulation and deposited on TiO2(110) and (ii) the possibility of taking advantage of the strong nanoparticle/support interactions present in this system to create patterned surfaces at the nanoscale. Following our approach, TiO2 nanostripes with tunable width, orientation, and uniform arrangement over large surface areas were produced

Shape-Selection of Thermodynamically Stabilized Colloidal Pd and Pt Nanoparticles Controlled via Support Effects

Colloidal chemistry, in combination with nanoparticle (NP)/support epitaxial interactions is used here to synthesize shape-selected and thermodynamically stable metallic NPs over a broad range of NP sizes. The morphology of three-dimensional palladium and platinum NPs supported on TiO₂(110) was investigated using scanning tunneling microscopy. Well-defined Pd and Pt NPs were synthesized via inverse micelle encapsulation. The initially spherical NPs were found to become faceted and form an epitaxial relationship with the support after high-temperature annealing (e.g., 1100 °C). Shape selection was achieved for almost all Pd NPs, namely, a truncated octahedron shape with (111) top and interfacial facets. The Pt NPs were however found to adopt a variety of shapes. The epitaxial relationship of the NPs with the support was evidenced by the alignment of the cluster’s edges with TiO₂(110)-[001] atomic rows and was found to be responsible for the shape control. The ability of synthesizing thermally stable shape-selected metal NPs demonstrated here is expected to be of relevance for applications in the field of catalysis, since the activity and selectivity of NP catalysts has been shown to strongly depend on the NP shape

Thermodynamic properties of Pt nanoparticles: Size, shape, support, and adsorbate effects

This study presents a systematic investigation of the thermodynamic properties of free and gamma-Al2O3-supported size-controlled Pt nanoparticles (NPs) and their evolution with decreasing NP size. A combination of in situ extended x-ray absorption fine-structure spectroscopy (EXAFS), ex situ transmission electron microscopy (TEM) measurements, and NP shape modeling revealed (i) a cross over from positive to negative thermal expansion with decreasing particle size, (ii) size- and shape-dependent changes in the mean square bond-projected bond-length fluctuations, and (iii) enhanced Debye temperatures (D-circle minus, relative to bulk Pt) with a bimodal size- dependence for NPs in the size range of similar to 0.8-5.4 nm. For large NP sizes (diameter d \u3e 1.5 nm) D-circle minus was found to decrease toward D-circle minus of bulk Pt with increasing NP size. For NPs \u3c = 1 nm, a monotonic decrease of D-circle minus was observed with decreasing NP size and increasing number of low-coordinated surface atoms. Our density functional theory calculations confirm the size- and shape-dependence of the vibrational properties of our smallest NPs and show how their behavior may be tuned by H desorption from the NPs. The experimental results can be partly attributed to thermally induced changes in the coverage of the adsorbate (H-2) used during the EXAFS measurements, bearing in mind that the interaction of the Pt NPs with the stiff, high-melting temperature gamma-Al2O3 support may also play a role. The calculations also provide good qualitative agreement with the trends in the mean square bond-projected bond-length fluctuations measured via EXAFS. Furthermore, they revealed that part of the D-circle minus enhancement observed experimentally for the smallest NPs (d \u3c = 1 nm) might be assigned to the specific sensitivity of EXAFS, which is intrinsically limited to bond-projected bond-length fluctuations

Anomalous lattice dynamics and thermal properties of supported size- and shape-selected Pt nanoparticles

Anomalous lattice dynamics and thermal behavior have been observed for ligand-free, size-, and shape-selected Pt nanoparticles (NPs) supported on nanocrystalline gamma-Al(2)O(3) via extended x-ray absorption fine-structure spectroscopy. Several major differences were observed for the NPs with respect to bulk Pt: (i) a contraction in the interatomic distances, (ii) a reduction in the dynamic (temperature-dependent) bond-length disorder and associated increase in the Debye temperature (theta(D)), and (iii) an overall decrease in the bond-length expansion coefficient coupled with NP stiffening. The increase in the Debye temperature is explained in terms of the NP size, shape, support interactions, and adsorbate effects. For a similar average size, we observe a striking correlation between the shapes of the NPs and their theta(D) values

Catalysing sustainable fuel and chemical synthesis

Concerns over the economics of proven fossil fuel reserves, in concert with government and public acceptance of the anthropogenic origin of rising CO2 emissions and associated climate change from such combustible carbon, are driving academic and commercial research into new sustainable routes to fuel and chemicals. The quest for such sustainable resources to meet the demands of a rapidly rising global population represents one of this century’s grand challenges. Here, we discuss catalytic solutions to the clean synthesis of biodiesel, the most readily implemented and low cost, alternative source of transportation fuels, and oxygenated organic molecules for the manufacture of fine and speciality chemicals to meet future societal demands

Nano Pinstripes: Tio 2 Nanostripe Formation By Nanoparticle-Mediated Pinning Of Step Edges

Over recent decades, abundant scientific evidence has led to authoritative dietary guidelines and recommendations for heart healthy eating and lifestyle behaviors. But most children and adults do not regularly achieve these goals. Consequently, our focus must now be on helping individual patients and our communities implement these guidelines in everyday life. This article reviews current evidence for insights and practical techniques that can help individuals move from ideal goals to real practice of heart healthy nutrition and lifestyle behaviors. © 2012 SAGE Publications

Nanoepitaxy using Micellar Nanoparticles

The shape of platinum and gold nanoparticles (NPs) synthesized via inverse micelle encapsulation and supported on TiO2(110) has been resolved by scanning tunneling microscopy. Annealing these systems at high temperature (∼1000 °C) and subsequent cooling to room temperature produced ordered arrays of well-separated three-dimensional faceted NPs in their equilibrium state. The observed shapes differ from the kinetically limited shapes of conventional physical vapor deposited NPs, which normally form two-dimensional flat islands upon annealing at elevated temperatures. The initial NP volume was found to provide a means to control the final NP shape. Despite the liquid-phase ex situ synthesis of the micellar particles, the in situ removal of the encapsulating ligands and subsequent annealing consistently lead to the development of a well-defined epitaxial relationship of the metal NPs with the oxide support. The observed epitaxial relationships could be explained in terms of the best overlap between the interfacial Pt (or Au) and TiO2 lattices. In most cases, the ratio of {100}/{111} facets obtained for the NP shapes resolved clearly deviates from that of conventional bulklike Wulff structures

Nanocatalysis: size- and shape-dependent chemisorption and catalytic reactivity

In recent years, the field of catalysis has experienced an astonishing transformation, driven in part by more demanding environmental standards and critical societal and industrial needs such as the search for alternative energy sources. Thanks to the advent of nanotechnology, major steps have been made towards the rational design of novel catalysts. Striking new catalytic properties, including greatly enhanced reactivities and selectivities, have been reported for nanoparticle (NP) catalysts as compared to their bulk counterparts. However, in order to harness the power of these nanocatalysts, a detailed understanding of the origin of their enhanced performance is needed. The present review focuses on the role of the NP size and shape on chemisorption and catalytic performance. Since homogeneity in NP size and shape is a prerequisite for the understanding of structure–reactivity correlations, we first review different synthesis methods that result in narrow NP size distributions and shape controlled NPs. Next, size-dependent phenomena which influence the chemical reactivity of NPs, including quantum size-effects and the presence of under-coordinated surface atoms are examined. The effect of the NP shape on catalytic performance is discussed and explained based on the existence of different atomic structures on the NP surface with distinct chemisorption properties. The influence of additional factors, such as the oxidation state of the NPs and NP–support interactions, is also considered in the frame of the size- and shape-dependency that these phenomena present. Ultimately, our review highlights the importance of achieving a systematic understanding of the factors that control the activity and selectivity of a catalyst in order to avoid trial and error methods in the rational design of the new generation of nanocatalysts with properties tunable at the atomic level