New Insights into Electronic and Geometric Effects in the Enhanced Photoelectrooxidation of Ethanol Using ZnO Nanorod/Ultrathin Au Nanowire Hybrids

Oxidation of small organic molecules in a fuel cell is a viable method for energy production. However, the key issue is the development of suitable catalysts that exhibit high efficiencies and remain stable during operation. Here, we demonstrate that amine-modified ZnO nanorods on which ultrathin Au nanowires are grown act as an excellent catalyst for the oxidation of ethanol. We show that the modification of the ZnO nanorods with oleylamine not only modifies the electronic structure favorably but also serves to anchor the Au nanowires on the nanorods. The adsorption of OH- species on the Au nanowires that is essential for ethanol oxidation is facilitated at much lower potentials as compared to bare Au nanowires leading to high activity. While ZnO shows negligible electrocatalytic activity under normal conditions, there is significant enhancement in the activity under light irradiation. We demonstrate a synergistic enhancement in the photoelectrocatalytic activity of the ZnO/Au nanowire hybrid and provide mechanistic explanation for this enhancement based on both electronic as well as geometric effects. The principles developed are applicable for tuning the properties of other metal/semiconductor hybrids with potentially interesting applications beyond the fuel cell application demonstrated here.

Room Temperature Growth of Ultrathin Au Nanowires with High Areal Density over Large Areas by in Situ Functionalization of Substrate

Although ultrathin Au nanowires (similar to 2 nm diameter) are expected to demonstrate several interesting properties, their extreme fragility has hampered their use in potential applications. One way to improve the stability is to grow them on substrates; however, there is no general method to grow these wires over large areas. The existing methods suffer from poor coverage and associated formation of larger nanoparticles on the substrate. Herein, we demonstrate a room temperature method for growth of these nanowires with high coverage over large areas by in situ functionalization of the substrate. Using control experiments, we demonstrate that an in situ functionalization of the substrate is the key step in controlling the areal density of the wires on the substrate. We show that this strategy works for a variety of substrates ranging like graphene, borosil glass, Kapton, and oxide supports. We present initial results on catalysis using the wires grown on alumina and silica beads and also extend the method to lithography-free device fabrication. This method is general and may be extended to grow ultrathin Au nanowires on a variety of substrates for other applications.

Synthesis and Characterization of Au@Pt Nanoparticles with Ultrathin Platinum Overlayers

Gold-core platinum-shell (Au@Pt) nanoparticles with ultrathin platinum overlayers, ranging from submonolayer to two monolayers of platinum atoms, were prepared at room-temperature using a scalable, wet-chemical synthesis route. The synthesis involved the reduction of chloroauric acid with tannic acid to form 5 nm (nominal dia.) gold nanoparticles followed by addition of desired amount of chloroplatinic acid and hydrazine to form platinum overlayers with bulk Pt/Au atomic ratios (Pt surface coverages) corresponding to 0.19 (half monolayer), 0.39 (monolayer), 0.58 (1.5 monolayer) and 0.88 (2 monolayers). The colloidal particles were coated with octadecanethiol and phase-transferred into chlroform-hexane mixture to facilitate sample preparation for structural characterization. The structure of the resultant nanoparticles were determined to be Au@Pt using HRTEM, SAED, XPS, UV-vis and confirmed by cyclic voltammetry (CV) studies. Monolayers of octadecanethiol coated Au@Pt nanoparticles were self-assembled at an air-water interface and transfer printed twice onto a gold substrate to form bilayer films for electrochemical characterization. Electrochemical activity on such films was observed only after the removal of the octadecanethiol ligand coating the nanoparticles, using a RF plasma etching process. The electrochemical activity (HOR, MOR studies) of Au@Pt nanoparticles was found to be highest for particles having a two atom thick platinum overlayer. These nanoparticles can significantly enhance platinum utilization in electrocatalytic applications as their platinum content based activity was three times higher than pure platinum nanoparticles.

Postsynthetic Exterior Decoration of an Organic Cage by Copper(I)-Catalysed A(3)-Coupling and Detection of Nitroaromatics

A new synthetic protocol based on one-pot, copper(I)-catalysed multicomponent reaction of formaldehyde, secondary amine and terminal alkyne has been employed to postsynthetically modify a self-assembled nanoscopic organic cage. By employing this synthetic strategy, three new cages appended with phenyl-, xylyl-and naphthyl-acetylene moieties have been synthesised. The resulting modified cages were characterised by using a range of spectroscopic techniques. The synthesised cages were fluorescent and thus one of them was tested to explore the potential use of such compounds as chemosensors for the detection of nitroaromatics. Experimental findings suggest a high selective quenching of initial fluorescence intensity in the presence of nitroaromatic compounds. Furthermore, it has been observed that among the various nitroaromatics tested, nitrophenolic compounds have better quenching ability.

Reversible Aptamer-Au Plasmon Rulers for Secreted Single Molecules

Plasmon rulers, consisting of pairs of gold nanoparticles, allow single-molecule analysis without photobleaching or blinking; however, current plasmon rulers are irreversible, restricting detection to only single events. Here, we present a reversible plasmon ruler, comprised of coupled gold nanoparticles linked by a single aptamer, capable of binding individual secreted molecules with high specificity. We show that the binding of target secreted molecules to the reversible plasmon ruler is characterized by single-molecule sensitivity, high specificity, and reversibility. Such reversible plasmon rulers should enable dynamic and adaptive live-cell measurement of secreted single molecules in their local microenvironment.

Morphology control synthesis of Au-Cu2S metal-semiconductor hybrid nanostructures by modulating reaction constituents

A facile methodology for synthesizing Au-Cu2S hybrid nanoparticles is presented. Au-Cu2S nanoparticles have application in visible light driven photocatalytic degradation of dyes. Detailed microstructural and compositional characterization illustrated that the hybrid nanoparticles are composed of cube shaped Au-Cu solid solution and hemispherical shaped Cu2S phases. Investigation of nanoparticles extracted at different stages of the synthesis process revealed that the mechanism of formation of hybrid nanoparticles involved initial formation of isolated cube shaped pure Au nanoparticles and Cu-thiolate complex. In the subsequent stages, the Au nanoparticles get adsorbed onto the Cu-thiolate complex which is followed by the decomposition of the Cu-thiolate complex to form Au-Cu2S hybrid nanoparticles. This study also illustrates that an optimum concentration of dodecanethiol is required both for achieving size and morphological uniformity of the participating phases and for their attachment to form a hybrid nanoparticle.

Ultrathin Au nanowires supported on rGO/TiO2 as an efficient photoelectrocatalyst

We report the synthesis of stable rGO/TiO2/Au nanowire hybrids showing excellent electrocatalytic activity for ethanol oxidation. Phase-pure anatase TiO2 nanoparticles (similar to 3 nm) were grown on GO sheets followed by the growth of ultrathin Au nanowires leading to the formation of a multidimensional ternary structure (0-D TiO2 and 1-D Au on 2-D graphene oxide). The oleylamine used for the synthesis of the Au nanowires not only leads to stable Au nanowires anchored on the GO sheets but also leads to the functionalization and room temperature reduction of GO. Using control experiments, we delineate the role of the three components in the hybrid and show that there is a significant synergy. We show that the catalytic activity for ethanol oxidation primarily stems from the Au nanowires. While TiO2 triggers the formation of oxygenated species on the Au nanowire surface at a lower potential and also imparts photoactivity, rGO provides a conducting support to minimize the charge transfer resistance in addition to stabilizing the Au nanowires. Compared with nanoparticle hybrids, the nanowire hybrids display a much better electrocatalytic performance. In addition to high efficiency, the nanowire hybrids also show a remarkable tolerance towards H2O2. While our study has a direct bearing on fuel cell technology, the insights gained are sufficiently general such that they provide guiding principles for the development of multifunctional ternary hybrids.

Graphene-oxide-supported ultrathin Au nanowires: efficient electrocatalysts for borohydride oxidation

We report stable ultrathin Au nanowires supported on reduced graphene oxide with outstanding electrocatalytic activity for borohydride oxidation. Electrochemical impedance spectroscopy measurements showed abnormal inductive behavior, indicative of surface reactivation. DFT calculations indicate that the origin of the high activity stems from the position of the Au d-band center.

Density control of ZnO nanowires grown using Au-PMMA nanoparticles and their growth behavior.

Au nanoparticles stabilized by poly(methyl methacrylate) (PMMA) were used as a catalyst to grow vertically aligned ZnO nanowires (NWs). The density of ZnO NWs with very uniform diameter was controlled by changing the concentration of Au-PMMA nanoparticles (NPs). The density was in direct proportion to the concentration of Au-PMMA NPs. Furthermore, the growth process of ZnO NWs using Au-PMMA NPs was systematically investigated through comparison with that using Au thin film as a catalyst. Au-PMMA NPs induced polyhedral-shaped bases of ZnO NWs separated from each other, while Au thin film formed a continuous network of bases of ZnO NWs. This approach provides a facile and cost-effective catalyst density control method, allowing us to grow high-quality vertically aligned ZnO NWs suitable for many viable applications.

Adlayer Structures of DL-Homocysteine and L-Homocysteine Thiolactone on Au(111) Surface: an in situ STM Study

The adsorption Of DL-homocysteine (Hcy) and L-homocysteine thiolactone (HTL) on Au(1 1 1) electrode was investigated in 0.1 M HClO4 by cyclic voltammetry and in situ scanning tunneling microscopy (STM). Hcy and HTL molecules formed highly ordered adlayers on Au(1 1 1) surface. High-resolution STM images revealed the orientation and packing arrangement in the ordered adlayers. Hcy molecules formed (2root3 x 3root3)R30degrees adlayer structure and H-bonds between carboxyl groups were assumed to be responsible for the origin of tail-to-tail or head-to-head molecular arrangement, while HTL molecules formed (4 x 6) adlayer structure, and two different orientations and appearances in the ordered adlayer were found. Structural models were proposed for the two adlayers.

Electrochemical, spectroscopic and SPM evidence for the controlled formation of self-assembled monolayers and organised multilayers of ferrocenyl alkyl thiols on Au(111)

Organised multilayers were formed from the controlled self-assembly of ferrocene alkyl thiols on Au(111) surfaces. The control was accomplished by increasing the concentration of the thiol solutions used for the assembly. Cyclic voltammetry, ellipsometry, scanning probe microscopy (STM and AFM) and in situ FTIR spectroscopy were used to probe the differences between mono- and multilayers of the same compounds. Electrochemical desorption studies confirmed that the multilayer structure is attached to the surface via one monolayer. The electrochemical behaviour of the multilayers indicated the presence of more than one controlling factor during the oxidation step, whereas the reduction was kinetically controlled which contrasts with the behaviour of monolayers, which exhibit kinetic control for the oxidation and reduction steps. Conventional and imaging ellipsometry confirmed that multilayers with well-defined increments in thickness could be produced. However, STM indicated that at the monolayer stage, the thiols used promote the mobility of Au atoms on the surface. It is very likely that the multilayer structure is held together through hydrogen bonding. To the best of out knowledge, this is the first example of a controlled one-step growth of multilayers of ferrocenyl alkyl thiols using self-assembly techniques.

Anisotropic Deformation Of Polystyrene Particles By Mev Au Ion Irradiation

MeV An irradiation leads to a shape change of polystyrene (PS) and SiO2 particles from spherical to ellipsoidal, with an aspect ratio that can be precisely controlled by the ion fluence. Sub-micrometer PS and SiO2 particles were deposited on copper substrates and irradiated with Au ions at 230 K, using an ion energy and fluence ranging from 2 to 10 MeV and 1 x 10(14) ions/cm(2) to 1 x 10(15) ions/cm(2). The mechanisms of anisotropic deformation of PS and SiO2 particles are different because of their distinct physical and chemical properties. At the start of irradiation, the volume of PS particles decrease, then the aspect ratio increases with fluence, whereas for SiO2 particles the volume remains constant. (C) 2008 Elsevier B.V. All rights reserved.

Influence Of Different Amount Of Au On The Wetting Behavior Of Pdms Membrane

Polydimethylsiloxane (PDMS) has been widely used as a base material for bio-MEMS/NEMS devices. It is difficult for PDMS to transfer and spread aqueous solution as a kind of highly hydrophobic material. Therefore, surface modification is necessary for PDMS to make it hydrophilic. In this paper, a method of hydrophilization of PDMS surface is proposed. Gold is sputtered to the PDMS substrate by sputter coater in different average thicknesses. Relationship between the average thickness of gold on the PDMS substrate and the contact angle of the surface was studied. It was found that even gold of average thickness less than 1 nm can result in about 25 degrees change of contact angle. AFM is also used to get topographic information of PDMS surface coated with gold. Three cases are classified with different amount of Au: (1) Heterogeneous zone; (2) Transition zone; (3) Film zone. For heterogeneous zone, a simple model about heterogeneous phase wetting is put forward to interpret this phenomenon.