Segmented All-Platinum Nanowires with Controlled Morphology through Manipulation of the Local Electrolyte Distribution in Fluidic Nanochannels during Electrodeposition

Synthesis of segmented all-Pt nanowires is achieved by a template-assisted method. The combination of a suitably chosen electrolyte/template system with pulse-reverse electrodeposition allows the formation of well-defined segments linked to nanowires. Manipulation of the morphology is obtained by controlling the electrokinetie effects on the local electrolyte distribution inside the nanochannels during the nanowire growth process, allowing a deviation from the continuously cylindrical geometry given by the nanoporous template. The length of the segments can be adjusted as a function of the cathodic pulse duration. Applying constant pulses leads to segments with homogeneous shape and dimensions along most of the total wire length. X-ray diffraction demonstrates that the preferred crystallite orientation of the polycrystalline wires varies with the average segment length. The results are explained considering transitions in texture formation with increasing thickness of the electrodeposit. A mechanism of segment formation is proposed based on structural characterizations. Nanowires with controlled segmented morphology are of great technological importance, because of the possibility to precisely control their substructure as a means of tuning their electrical, thermal, and optical properties. The concept we present in this work for electrodeposited platinum and track-etched polycarbonate membranes can be applied to other selected materials as well as templates and constitutes a general method to controlled nanostructuring and synthesis of shape controlled nanostructures.

Benzene electro-oxidation in a PEMFC for phenol and electricity cogeneration

In the present investigation, the electrochemically-assisted oxidation of benzene in a H-2-O-2 proton exchange membrane fuel cell (PEMFC) for electricity and phenol cogeneration is studied. Experiments were carried out in a PEMFC electrochemical reactor using Pd black as cathode electrocatalyst at 60 and 80 degrees C, respectively and 1 atm back pressure. Indeed, it was found that the only product detected under the examined experimental conditions was phenol. The online GC product analysis revealed that it is impossible to produce phenol when the fuel cell circuit is open (I = 0) under all the examined experimental conditions. When the fuel cell circuit was closed, however, the phenol yield was found to follow a volcano-type dependence on the cur-rent of the external circuit. It was found that the maximum phenol yield was 0.35% at 100 mA/cm(2) at 80 degrees C. At the same time, the PEMFC performance was also investigated during the phenol generation process. Furthermore, experiments with the rotating ring disc electrode (RRDE) technique showed that the intermediate oxidation product, i.e. H2O2 existed during the oxygen electro-reduction process. The cyclic voltammograms showed that benzene was strongly adsorbed on the Pd surface, leading to a degradation of the PEMFC performance. (c) 2005 Elsevier B.V. All rights reserved.

Controllable synthesis of metal hydroxide and oxide nanostructures by ionic liquids assisted electrochemical corrosion method

Cu(OH)(2) nanowires have been synthesized by anodic oxidation of copper through a simple electrolysis process employing ionic liquid as an electrolyte. Controlling the electrochemical conditions can qualitatively modulate the lengths, amounts, and shapes of Cu(OH)(2) nanostructures. A rational mechanism based on coordination self-assembly and oriented attachment is proposed for the selective formation of the polycrystalline Cu(OH)(2) nanowires. In addition, the FeOOH nanoribbons, Ni(OH)(2) nanosheets, and ZnO nanospheres were also synthesized by this route, indicative of the universality of the electrochemical route presented herein. The morphologies and structures of the synthesized nanostructures have been characterized by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), powder X-ray diffraction (XRD). Fourier transform infrared spectra (FT-IR), and thermogravimetric (TG). (C) 2007 Elsevier Masson SAS. All rights reserved

A New Method for Analysis of Disulfide-Containing Proteins by Matrix-Assisted Laser Desorption Ionization (MALDI) Mass Spectrometry

A simple and high-throughput method for the identification of disulfide-containing peptides utilizing peptide-matrix adducts is described. Some commonly used matrices in MALDI mass spectrometry were found to specifically react with sulfhydryl groups within peptide, thus allowing the observation of the peptide-matrix adduct ion [M + n + n' matrix + H](+) or [M + n + n' matrix + Na](+) (n = the number of cysteine residues, n' = 1, 2, ..., n) in MALDI mass spectra after chemical reduction of disulfide-linked peptides. Among several matrices tested, alpha-cyano-4-hydroxycinnamic acid (CHCA, molecular mass 189 Da) and alpha-cyano-3-hydroxycinnamic acid (3-HCCA) were found to be more effective for MALDI analysis of disulfide-containing peptides/proteins. Two reduced cysteines involved in a disulfide bridge resulted in a mass shift of 189 Da per cysteine, so the number of disulfide bonds could then be determined, while for the other matrices (sinapinic acid, ferulic acid, and caffeic acid), a similar addition reaction could not occur unless the reaction was carried out under alkaline conditions. The underlying mechanism of the reaction of the matrix addition at sulfhydryl groups is proposed, and several factors that might affect the formation of the peptide-matrix adducts were investigated.

Engineering white light-emitting Eu-doped ZnO urchins by biopolymer-assisted hydrothermal method

With the presence of biopolymer-sodium alginate as additive, Eu-doped ZnO (zinc oxide) urchins consisting of nanorods were synthesized through a hydrothermal route. X-ray diffraction pattern makes evident the absence of phase other than wurtzite ZnO. Upon excited by 325 nm xenon laser, such nanostructured Eu-doped ZnO urchins emit white light, which originates from the luminescence of ZnO and the intra-4f transitions of Eu3+ ions. Besides acting as stabilizing agent, sodium alginate may also sensitize the Eu3+ ions in the nanostructures and facilitate the energy transfer from the host to Eu3+ ions. (c) 2006 American Institute of Physics.

Rapidly Infrared-Assisted Cooperatively Self-Assembled Highly Ordered Multiscale Porous Materials

In this paper, cooperative self-assembly (CSA) of colloidal spheres with different sizes was studied. It was found that a complicated jamming effect makes it difficult to achieve an optimal self-assembling condition for construction of a well-ordered stacking of colloidal spheres in a relatively short growth time by CSA. Through the use of a characteristic infrared (IR) technique to significantly accelerate local evaporation on the growing interface without changing the bulk growing environment, a concise three-parameter (temperature, pressure, and IR intensity) CSA method to effectively overcome the jamming effect has been developed. Mono- and multiscale inverse opals in a large range of lattice scales can be prepared within a growth time (15-30 min) that is remarkably shorter than the growth times of several hours for previous methods. Scanning electron microscopy images and transmittance spectra demonstrated the superior crystalline and optical qualities of the resulting materials. More importantly, the new method enables optimal conditions for CSA without limitations on sizes and materials of multiple colloids. This strategy not only makes a meaningful advance in the applicability and universality of colloidal crystals and ordered porous materials but also can be an inspiration to the self-assembly systems widely used in many other fields, such as nanotechnology and molecular bioengineering.

Pressure-assisted field-amplified sample injection with reverse migrating micelles for analyzing trace steroids in MEKC

This paper describes a novel method that applies pressure-assisted field-amplified sample injection with reverse migrating micelles (PA-FASI-RMM) for the online concentration of neutral analytes in MEKC with a low-pH BGE. After injection of a plug of water into the separation capillary, negative voltage and positive pressure were simultaneously applied to initialize PA-FASI-RMM injection. The hydrodynamic flow generated by the positive pressure compensated the reverse EOF in the water plug and allowed the water plug to remain in the capillary during FASI with reverse migrating micelles (FASI-RMM) to obtain a much longer injection time than usual, which improved stacking efficiency greatly. Equations describing this injection mode were introduced and were supported by experimental results. For a 450-s online PA-FASI-RMM injection, three orders of magnitude sample enhancement in terms of peak area could be observed for the steroids and an achievement of detection limits was between 1 and 10 ng/mL.

Fabrication of Silicon-Based Template-Assisted Nanoelectrode Arrays and Ohmic Contact Properties Investigation

A convenient fabrication technology for large-area, highly-ordered nanoelectrode arrays on silicon substrate has been described here, using porous anodic alumina (PAA) as a template. The ultrathin PAA membranes were anodic oxidized utilizing a two-step anodization method, from Al film evaporated on substrate. The purposes for the use of two-step anodization were, first, improving the regularity of the porous structures, and second reducing the thickness of the membranes to 100 similar to 200 nm we desired. Then the nanoelectrode arrays were obtained by electroless depositing Ni-W alloy into the through pores of PAA membranes, making the alloy isolated by the insulating pore walls and contacting with the silicon substrates at the bottoms of pores. The Ni-W alloy was also electroless deposited at the back surface of silicon to form back electrode. Then ohmic contact properties between silicon and Ni-W alloy were investigated after rapid thermal annealing. Scanning electron microscopy (SEM) observations showed the structure characteristics, and the influence factors of fabrication effect were discussed. The current voltage (I-V) curves revealed the contact properties. After annealing in N-2 at 700 degrees C, good linear property was shown with contact resistance of 33 Omega, which confirmed ohmic contacts between silicon and electrodes. These results presented significant application potential of this technology in nanosize current-injection devices in optoelectronics, microelectronics and bio-medical fields.

Microwave-assisted hydrothermal synthesis of hydroxy-sodalite zeolite membrane

A high quality pure hydroxy-sodalite zeolite membrane was successfully synthesized on an alpha-Al2O3 support by a novel microwave-assisted hydrothermal synthesis (MARS) method. Influence of synthesis conditions, such as synthesis time, synthesis procedure, etc., on the formation of hydroxy-sodalite zeolite membrane by MAHS method was studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and gas permeation measurements. The synthesis of hydroxy-sodalite zeolite membrane by MAHS method only needed 45 min and synthesis was more than 8 times faster than by the conventional hydrothermal synthesis (CHS) method. A pure hydroxy-sodalite zeolite membrane was easily synthesized by MAHS method, while a zeolite membrane, which consisted of NaX zeolite, NaA zeolite and hydroxy-sodalite zeolite, was usually synthesized by CHS method. The effect of preparation procedures had a dramatic impact on the formation of hydroxy-sodalite zeolite membrane and a single-stage synthesis procedure produced a pure hydroxy-sodalite zeolite membrane. The pure hydroxy-sodalite zeolite membrane synthesized by MARS method was found to be well inter-grown and the thickness of the membrane was 6-7 mum. Gas permeation results showed that the hydrogen/n-butane permselectivity of the hydroxy-sodalite zeolite membrane was larger than 1000. (C) 2004 Elsevier Inc. All rights reserved.

Enzymatic reaction of the immobilized enzyme on porous silicon studied by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry

Desorption/ionization on silicon mass spectrometry (DIOS-MS) is a matrix-free technique that allows for the direct desorption/ionization of low-molecular-weight compounds with little or no fragmentation of analytes. This technique has a relatively high tolerance for contaminants commonly found in biological samples. DIOS-MS has been applied to determine the activity of immobilized enzymes on the porous silicon surface. Enzyme activities were also monitored with the addition of a competitive inhibitor in the substrate solution. It is demonstrated that this method can be applied to the screening of enzyme inhibitors. Furthermore, a method for peptide mapping analysis by in situ digestion of proteins on the porous silicon surface modified by trypsin, combined with matrix-assisted laser desorption/ionization-time of flight-MS has been developed.

Epitaxy-Assisted Creation of PCBM Nanocrystals and Its Application in Constructing Optimized Morphology for Bulk-Heterojunction Polymer Solar Cells

PCBM (a C-60 derivative) is so far the most successful electron acceptor for bulk-heterojunction polymer photovoltaic (PV) cells. Here we present a novel method epitaxy-assisted creation of PCBM nanocrystals and their homogeneous distribution in the matrix using freshly cleaved mica sheet as the substrate. The highly matched epitaxy relationship between the unit cell of PCBM crystal and crystallographic (001) surface of mica induces abundant PCBM nuclei, which subsequently develop into nanoscale crystals with homogeneous dispersion in the composite film.

3D Fe3S4 flower-like microspheres: high-yield synthesis via a biomolecule-assisted solution approach, their electrical, magnetic and electrochemical hydrogen storage properties

Well-defined 3D Fe3S4 flower-like microspheres were synthesized via a simple biomolecule-assisted hydrothermal process for the first time. On the basis of a series of contrast experiments, the probable growth mechanism and fabrication process of the products were proposed. The electrical conductivity property of the as-synthesized Fe3S4 sample exhibited a rectifying characteristic when a forward bias was applied for the bottom-contacted device. The magnetic properties of the products were studied as well and the results demonstrated that the products presented ferromagnetic properties related to the corresponding microstructure. In addition, we first verified that the Fe3S4 flower-like microspheres could store hydrogen electrochemically, and a discharge capacity of 214 mA h g(-1) was measured without any activation under normal atmospheric conditions at room temperature.

A method for quantitative analysis of nitrogen oxides and N2 by means of mass spectrometry with the assistance of a catalytic technique for the reduction of NO with CO or hydrocarbons

Mass spectrometry is not able to differentiate NOx and N2 from other interferences (e.g. CO and C2H4) in the deNOx reactions. In the present study, a quantitative method for analysis of NOx and N2 simultaneously in these reactions with an assisted converter operated at higher temperature under O2-rich condition, which eliminates the interferences, is developed. The NOx conversion from this method is comparable to the one from an Automotive Emission Analyser equipped with NOx electrochemical sensor. Two types of deNOx reactions are tested in terms of selectivity of N2 production. The application of this method is discussed.