Orientation dependent electrocatalysis using self-assembled molecular films

Surface orientation of self-assembled molecular films of 2,9,6,23-tetraamino cobalt phthalocyanine on gold and silver is shown to determine the nature and the products of the electrocatalytic reduction of oxygen.

Self-assembled molecular films of tetraamino metal (Co, Cu, Fe) phthalocyanines on gold and silver. Electrochemical and spectroscopic characterization

The formation of molecular films of 2,9,16,23-tetraamino metal phthalocyanines [TAM(II)Pc; M (II) = Co, Cu, and TAM(III)Pc; M = Fe] by spontaneous adsorption on gold and silver surfaces is described. The properties of these films have been investigated by cyclic voltammetry, impedance, and FT-Raman spectroscopy. The charge associated with Co(II) and Co(I) redox couple in voltammetric data leads to a coverage of (0.35+/-0.05) x 10(-10) mol cm(-2), suggesting that the tetraamino cobalt phthalocyanine is adsorbed as a monolayer with an almost complete coverage. The blocking behavior of the films toward oxygen and Fe(CN)(6)(3-/4-) redox couple have been followed by cyclic voltammetry and impedance measurements. This leads to an estimate of the coverage of about 85 % in the case of copper and the iron analogs. FT-Raman studies show characteristic bands around 236 cm(-1) revealing the interaction between the metal substrate and the nitrogen of the -NH2 group on the phthalocyanine molecules.

Crystallization of SrCO3 on a self-assembled monolayer substrate: an in-situ synchrotron X-ray study

Self-assembled monolayers (SAMs) of alkanethiols on gold surfaces show great promise in controlling the nucleation and growth of inorganic minerals from solution. In doing so, they mimic the role of some biogenic macromolecules in natural biomineralisation processes. Crystallization on SAM surfaces is usually monitored ex-situ; by allowing the process to commence and to evolve for some time, removing the substrate from the mother solution, and then examining it using microscopy, diffraction etc. We present here for the first time, the use of high energy monochromatic synchrotron X-radiation in conjunction with a two dimensional detector to monitor in situ, in a time resolved fashion, the growth of SrCO3 (strontianite) crystals on a SAM substrate.

Self-assembled microtubes and rhodamine 6G functionalized Raman-active gold microrods from 1-hydroxybenzotriazole

1-Hydroxybenzotriazole spontaneously self-assembles to form hollow, linear microtubes initiated by controlled evaporation from water. The tube cavities act as thermo-labile micromoulds for the synthesis of linear gold microrods. Rhodamine 6G-labelled gold microrods, exhibiting surface enhanced resonance Raman activity, have been synthesized using the HOBT microtubes.

Stress induced phase transition in a monomolecular perfluroalkylsilane film self assembled on aluminium surface

We control the stiffnesses of two dual double cantelevers placed in series to control penetration into a perflurooctyltrichlorosilane monolayer self assembled on aluminium and silicon substrates. The top cantilever which carries the probe is displaced with respect to the bottom cantilever which carries the substrate, the difference in displacement recorded using capacitors gives penetration. We further modulate the input displacement sinusoidally to deconvolute the viscoelastic properties of the monolayer. When the intervention is limited to the terminal end of the molecule there is a strong viscous response in consonance with the ability of the molecule to dissipate energy by the generation of gauche defects freely. When the intervention reaches the backbone, at a contact mean pressure of 0.2GPa the damping disappears abruptly and the molecule registers a steep rise in elastic modulus and relaxation time constant, with increasing contact pressure. We offer a physical explanation of the process and describe this change as due to a phase transition from a liquid like to a solid like state.

Scalable processes for fabricating non-volatile memory devices using self-assembled 2D arrays of gold nanoparticles as charge storage nodes

We propose robust and scalable processes for the fabrication of floating gate devices using ordered arrays of 7 nm size gold nanoparticles as charge storage nodes. The proposed strategy can be readily adapted for fabricating next generation (sub-20 nm node) non-volatile memory devices.

Self Assembled Monolayers of Alkanethiolson Silver Surfaces

This short review compiles the studies on self assembled alkanethiol monolayers formed on silver surfaces with respect to their structure and stability. Alkanethiol-based assemblies on silver surfaces are poor cousins of thiol monolayers on gold. The formation of well-ordered monolayers on silver surfaces is relatively more difficult than the corresponding systems on gold since the inherent oxide film on silver interferes with the formation and stability of the assembly. There are contradictory reports on the nature and physicochemical characteristics of alkanethiol monolayers on silver surfaces. This review attempts to highlight various studies in the literature including our efforts in this area.

Synthesis and characterization of self-assembled nanofiber-bundles of V(2)O(5): their electrochemical and field emission properties

High-quality self-assembled V(2)O(5) nanofiber-bundles (NBs) are synthesized by a simple and direct hydrothermal method using a vanadium(V) hydroxylamido complex as a vanadium source in the presence of HNO(3). The possible reaction pathway for the formation of V(2)O(5) NBs is discussed and demonstrated that HNO(3) functions both as an oxidizing and as an acidification agent. V(2)O(5) NBs are single-crystals of an orthorhombic phase that have grown along the [010] direction. A bundle is made of indefinite numbers of homogeneous V(2)O(5) nanofibers where nanofibers have lengths up to several micrometres and widths ranging between 20 and 50 nm. As-prepared V(2)O(5) NBs display a high electrochemical performance in a non-aqueous electrolyte as a cathode material for lithium ion batteries. Field emission properties are also investigated which shows that a low turn-on field of similar to 1.84 V mu m(-1) is required to draw the emission current density of 10 mu Lambda cm(-2).

Layer-by-Layer Self-Assembled Metal-Ion- (Ag-, Co-, Ni-, and Pd-) Doped TiO2 Nanoparticles: Synthesis, Characterisation, and Visible Light Degradation of Rhodamine B

Metal-ion- (Ag, Co, Ni and Pd) doped titania nanocatalysts were successfully deposited on glass slides by layer-by-layer (LbL) self-assembly technique using a poly(styrene sulfonate sodium salt) (PSS) and poly(allylamine hydrochloride) (PAH) polyelectrolyte system. Solid diffuse reflectance (SDR) studies showed a linear increase in absorbance at 416 nm with increase in the number of m-TiO2 thin films. The LbL assembled thin films were tested for their photocatalytic activity through the degradation of Rhodamine B under visible-light illumination. From the scanning electron microscope (SEM), the thin films had a porous morphology and the atomic force microscope (AFM) studies showed ``rough'' surfaces. The porous and rough surface morphology resulted in high surface areas hence the high photocatalytic degradation (up to 97% over a 6.5 h irradiation period) using visible-light observed. Increasing the number of multilayers deposited on the glass slides resulted in increased film thickness and an increased rate of photodegradation due to increase in the availability of more nanocatalysts (more sites for photodegradation). The LbL assembled thin films had strong adhesion properties which made them highly stable thus displaying the same efficiencies after five (5) reusability cycles.

Self-Assembled Pd6 Open Cage with Triimidazole Walls and the Use of Its Confined Nanospace for Catalytic Knoevenagel- and Diels-Alder Reactions in Aqueous Medium

The two-component self-assembly of a 90 degrees PdII acceptor and a triimidazole donor led to the formation of a water-soluble semi-cylindrical cage with a hydrophobic cavity, which was separately crystallized with hydrophilic- and hydrophobic guests. The parent cage was found to catalyze the Knoevenagel condensation reaction of a series of aromatic mono-aldehydes with active methylene compounds, such as Meldrum's acid or 1,3-dimethylbarbituric acid. The confined hydrophobic nanospace within this cage was also used in the catalytic DielsAlder reactions of 9-hydroxymethylanthracene with N-phenylmaleimide or N-cyclohexylmaleimide.

Fabrication of Highly Dense Nanoholes by Self-Assembled Gallium Droplet on Silicon Surface

We report the fabrication of nanoholes on silicon surface by exploiting the solubility of silicon in gallium by local droplet etching. Nanometer-sized gallium droplets yield nanoholes when annealed in ultra-high vacuum at moderate temperatures (similar to 500 degrees C) without affecting the other regions. High vacuum and moderate annealing temperatures are key parameters to obtain well-defined nanoholes with diameter comparable to that of Ga droplets. Self-assembly of Ga droplet leads to a nanohole density of 4-8 x 10(10)/cm(2).

Multi-component, Self-assembled, Functional Soft Materials

Supramolecular chemistry is an emerging tool for devising materials that can perform specified functions. The self-assembly of facially amphiphilic bile acid molecules has been extensively utilized for the development of functional soft materials. Supramolecular hydrogels derived from the bile acid backbone act as useful templates for the intercalation of multiple components. Based on this, synthesis of gel-nanoparticle hybrid materials, photoluminescent coating materials, development of a new enzyme assay technique, etc. were achieved in the author's laboratory. The present account highlights some of these achievements.

Pt-Ru decorated self-assembled TiO2-carbon hybrid nanostructure for enhanced methanol electrooxidation

Porous titanium oxide-carbon hybrid nanostructure (TiO2-C) with a specific surface area of 350 m(2)/g and an average pore-radius of 21 center dot 8 is synthesized via supramolecular self-assembly with an in situ crystallization process. Subsequently, TiO2-C supported Pt-Ru electro-catalyst (Pt-Ru/TiO2-C) is obtained and investigated as an anode catalyst for direct methanol fuel cells (DMFCs). X-ray diffraction, Raman spectroscopy and transmission electron microscopy (TEM) have been employed to evaluate the crystalline nature and the structural properties of TiO2-C. TEM images reveal uniform distribution of Pt-Ru nanoparticles (d (Pt -aEuro parts per thousand Ru) = 1 center dot 5-3 center dot 5 nm) on TiO2-C. Methanol oxidation and accelerated durability studies on Pt-Ru/TiO2-C exhibit enhanced catalytic activity and durability compared to carbon-supported Pt-Ru. DMFC employing Pt-Ru/TiO2-C as an anode catalyst delivers a peak-power density of 91 mW/cm(2) at 65 A degrees C as compared to the peak-power density of 60 mW/cm(2) obtained for the DMFC with carbon-supported Pt-Ru anode catalyst operating under similar conditions.

Micro-Raman and photoluminescence studies of self-assembled quantum well microtubes on GaAs substrate

The Semiconductor Quantum Well (QW) microtubes have been fabricated by strain-induced self assembling technique. Three types of multilayer structures have consisted of GaAs/InxGa1-xAs strained layers containing with various thickness of Monolayers of (GaAs/AlGaAs) QW were grown by Varian Gen II Molecular Beam Epitaxy (MBE) on the GaAs (100) substrate. The shape of the rolled up microtubes provide a clear idea about the formation of three dimensional micro- and nanostructures. Micro-Raman and photoluminescence (PL) studies were performed to the QW microtubes and as compared with their grown area on the GaAs substrate. The results of Raman spectra show the frequency shift of phonon modes measured in tube and compared with the grown area due to residual strain. The PL peaks of the microtube were red-shifted due to the strain effect and transition of bandgap from Type-II to Type-I. (C) 2013 Elsevier B.V. All rights reserved.