Unprecedented transformation of tetrathienoanthracene into pentacene on Ni(111)

The imaging and characterization of single-molecule reaction events is essential to both extending our basic understanding of chemistry and applying this understanding to challenges at the frontiers of technology, for example, in nanoelectronics. Specifically, understanding the behavior of individual molecules can elucidate processes critical to the controlled synthesis of materials for applications in multiple nanoscale technologies. Here, we report the synthesis of an important semiconducting organic molecule through an unprecedented reaction observed with submolecular resolution by scanning tunneling microscopy (STM) under ultrahigh vacuum (UHV) conditions. Our images reveal a sulfur abstraction and cyclization reaction that converts tetrathienoanthracene precursors into pentacene on the Ni(111) surface. The identity of the final reaction product was confirmed by time-of-flight secondary ion mass spectrometry (TOF-SIMS). This reaction has no known literature analogue, and highlights the power of local-probe techniques for exploring new chemical pathways.

Thermal evolution of the submonolayer near-surface alloy of ZnPd on Pd (111)

We have performed a high-resolution synchrotron radiation photoelectron spectroscopy study of the initial growth stages of the ZnPd near-surface alloy on Pd(111), complemented by scanning tunnelling microscopy data. We show that the chemical environment for surfaces containing less than half of one monolayer of Zn is chemically distinct from subsequent layers. Surfaces where the deposition is performed at room temperature contain ZnPd islands surrounded by a substrate with dilute Zn substitutions. Annealing these surfaces drives the Zn towards the substrate top-layer, and favours the completion of the first 1 : 1 monolayer before the onset of growth in the next layer.

Indium clusters on the Ge (5× 5) wetting layer of Si (111)- 7× 7

The adsorption of In on the Si(111)−Ge(5×5) surface reconstruction has been studied with scanning tunneling microscopy and ab initio calculations to investigate the possibility of using this reconstruction as a template for cluster formation. As with In adsorption on Si(111)−7×7 at low substrate temperatures and low In fluences, the In adatoms are found to preferentially adsorb on the faulted half-unit cell. However, in contrast to In adsorption on Si(111)−7×7, the In adatoms are also frequently found in the unfaulted half-unit cell at low coverages. The filling of unfaulted unit cell halves is primarily due to the formation of large clusters that span multiple substrate half-unit cells. Moreover, many of the faulted half-unit cells have a streaked appearance that indicates that surface atoms within them are mobile.

Wrinkling of Atomic Planes in Ultrathin Au Nanowires

A detailed understanding of structure and stability of nanowires is critical for applications. Atomic resolution imaging of ultrathin single crystalline Au nanowires using aberration-corrected microscopy reveals an intriguing relaxation whereby the atoms in the close-packed atomic planes normal to the growth direction are displaced in the axial direction leading to wrinkling of the (111) atomic plane normal to the wire axis. First-principles calculations of the structure of such nanowires confirm this wrinkling phenomenon, whereby the close-packed planes relax to form saddle-like surfaces. Molecular dynamics studies of wires with varying diameters and different bounding surfaces point to the key role of surface stress on the relaxation process. Using continuum mechanics arguments, we show that the wrinkling arises due to anisotropy in the surface stresses and in the elastic response, along with the divergence of surface-induced bulk stress near the edges of a faceted structure. The observations provide new understanding on the equilibrium structure of nanoscale systems and could have important implications for applications in sensing and actuation.

Crystallographically driven Au catalyst movement during growth of InAs/GaAs axial nanowire heterostructures

The movement of Au catalysts during growth of InAs on GaAs nanowires has been carefully investigated by transmission electron microscopy. It has been found that Au catalysts preferentially stay on { 112 } B GaAs sidewalls. Since a {112} surface is composed of a {111} facet and a {002} facet and since {111} facets are polar facets for the zinc-blende structure, this crystallographic preference is attributed to the different interface energies caused by the different polar facets. We anticipate that these observations will be useful for the design of nanowire heterostructure based devices. © 2009 American Institute of Physics.

贵金属（Au, Ag, Pt, Pd）纳米材料的可控合成及性能研究

功能化的贵金属纳米材料的设计和可控制备在材料科学研究领域引起了人们广泛的关注。贵金属纳米材料的光学、电学、磁学和催化等物理和化学性质不但与其大小有关，而且还与其形貌息息相关。因此寻求简单而有效的低温溶液合成途径以实现对贵金属纳米材料的尺寸和形貌控制尤为重要。本论文的主要研究内容可以归纳如下： (1)在水溶液中利用种子生长方法分别制备了核壳Au-Pd/Pt三金属复合纳米粒子和三层的核壳AuAg复合纳米粒子。这些纳米粒子的尺寸和组成可以通过改变金种子的加入量来加以调控。 (2)通过种子生长和取代沉积相结合的方法制备了具有金核铂/银双金属壳的铃铛状纳米粒子。通过扫描电子显微镜、透射电子显微镜和X-射线光电子能谱对所得纳米粒子的尺寸、结构和组成进行了表征。 (3)以二肽甘氨酰甘氨酸作为模板合成了具有[111]取向的单晶银纳米片。通过改变实验条件探讨了片状银纳米结构的形成机理。片状银纳米结构的产率可达到80%，反应物之间的摩尔比对产物的尺寸和形貌有至关重要的作用。 (4)将K3[Fe(CN)6]和Na2S2O3的混合溶液进行水热处理，得到了具有立方体形貌的FeIIIFeIII(CN)6（柏林绿）微晶。实验结果显示K3[Fe(CN)6]和Na2S2O3的摩尔比及其浓度对所得产物的尺寸、形貌和组成有决定性的作用。 (5)在室温下通过混合3, 3', 5, 5'-四甲基联苯胺和氯铂酸，成功合成了有机-无机杂化的纳米纤维。纳米纤维的尺寸和形状可以通过改变反应物的比和浓度加以控制。基于不同的实验结果，提出了纳米纤维的可能形成机理。

Electrochemical designing of Au/Pt core shell nanoparticles as nanostructured catalyst with tunable activity for oxygen reduction

Au/Pt core shell nanoparticles (NPs) have been prepared via a layer-by-layer growth of Pt layers on An NPs using underpotential deposition (UPD) redox replacement technique. A single UPD Cu monolayer replacement with Pt(11) yielded a uniform Pt film on Au NPs, and the shell thickness can be tuned by controlling the number of UPD redox replacement cycles. Oxygen reduction reaction (ORR) in air-saturated 0.1 M H2SO4 was used to investigate the electrocatalytic behavior of the as-prepared core shell NPs. Cyclic voltammograms of ORR show that the peak potentials shift positively from 0.32 V to 0.48 V with the number of Pt layers increasing from one to five, suggesting the electrocatalytic activity increases with increasing the thickness of Pt shell. The increase in electrocatalytic activity may originate mostly from the large decrease of electronic influence of Au cores on surface Pt atoms. Rotating ring-disk electrode voltammetry and rotating disk electrode voltammetry demonstrate that ORR is mainly a four-electron reduction on the as-prepared modified electrode with 5 Pt layers and first charge transfer is the rate-determining step.

Progressive loss of ferroelectricity under bipolar pulsed fields and experimental determination of non-switchable polarization in Au/Ba0.5Sr0.5TiO3/SrRuO3 thin-film capacitors

175 nm-thick Ba0.5Sr0.5TiO3 (BST) thin film fabricated by pulsed laser deposition (PLD) technique is found to be a mixture of two distributions of material. We discuss whether these two components are nano-regions of paraelectric and ferroelectric phases, or a bimodal grain-size distribution, or an effect of oxygen vacancy gradient from the electrode interface. The fraction of switchable ferroelectric phase decreases under bipolar pulsed fields, but it recovers after removal of the external fields. The plot of capacitance in decreasing dc voltage (C(Vdown arrow) versus that in increasing dc 61 voltage C(Vup arrow) is a superposition of overlapping of two triangles, in contrast to one well-defined triangle for typical ferroelectric SrBi2Ta2O9 thin films.

Origin of the Increase of Activity and Selectivity of Nickel Doped by Au, Ag, and Cu for Acetylene Hydrogenation

Activity and selectivity are both important issues in heterogeneous catalysis and recent experimental results have shown that Ni catalysts doped by gold exhibit high activity for the hydrogenation of acetylene with good selectivity of ethylene formation. To unravel the underlying mechanism for this observation, the general trend of activity and selectivity of Ni surfaces doped by Au, Ag, and Cu has been investigated using density functional theory calculations. Complete energy profiles from C2H2 to C2H4 on Ni(111), Au/Ni(111), Ag/Ni(111) and Cu/Ni(111) are obtained and their turnover frequencies (TOFs) are computed. The results show that acetylene adsorption on Ni catalyst is strong which leads to the low activity while the doping of Au, Ag, and Cu on the Ni catalyst weakens the acetylene adsorption, giving rise to the increase of activity. The selectivity of ethylene formation is also quantified by using the energy difference between the hydrogenation barriers and the absolute value of the adsorption energies of ethylene. It is found that the selectivity of ethylene formation increases by doping Au and Ag, while those of Cu/Ni and Ni are similar.

Deactivation mechanism of a Au/CeZrO4 catalyst during a low-temperature water gas shift reaction

On-stream deactivation during a water gas shift (WGS) reaction over gold supported on a ceria-zirconia catalyst was examined. Although the fresh catalyst has very high low temperature (<200 degrees C) for WGS activity, a significant loss of CO conversion is found under steady-state operations over hours. This has been shown to be directly related to the concentration of water in the gas phase. The same catalyst also undergoes thermal deactivation above 250 degrees C, and using a combined experimental and theoretical approach, a common deactivation mechanism is proposed. In both cases, the gold nanoparticles, which are found under reaction conditions, are thought to detach from the oxide support either through hydrolysis, <200 degrees C, or thermally, > 200 degrees C. This process reduces the metal-support interaction, which is considered to be critical in determining the high activity of the catalyst.

One-Pot, High-Yield Synthesis of Convex Au Octahedra by H2O2 - Mediated Process In Solution Phase

A simple, non-seeding and high-yield synthesis of convex gold octahedra with size of ca. 50 nm in aqueous solution is described. The octahedral nanoparticles were systematically prepared by reduction of HAuCl4 using ascorbic acid (AA) in the presence of cetyltrimethylammonium bromide (CTAB) as the stabilizing surfactant while concentrations of Au3+ were fixed. The synthesizing process is especially different to other wet synthesis of metallic nanoparticles because it is mediated by H2O2. Mechanism of the H2O2 – mediated process will be described in details. The gold octahedra were shown to be single crystals with all 8 faces belonging to {111} family. Moreover, the single crystalline particles also showed attractive optical properties towards LSPR that should find uses as labels for microscopic imaging, materials for colorimetric biosensings, or nanosensor developments.

Aveux rendus au vicomte de Turenne.

Acquis le 30 octobre 1830 de M. Techener, libraire à Paris, parmi 23 volumes, pour le prix global de 400 francs; cf. B.n.F., département des Manuscrits, registre des acquisitions 1828-1833, n° 76/4 "terrier d'Agnet de La Tour et Annette de Beaufort, comtes de Beaufort, en 1459, folio"