Electrocatalytic oxidation of ascorbic acid using a single layer of gold nanoparticles immobilized on 1,6-hexanedithiol modified gold electrode

This paper describes the electrocatalytic oxidation of ascorbic acid (AA) in phosphate buffer solution by the immobilized citrate capped gold nanoparticles (AuNPs) on 1,6-hexanedithiol (HDT) modified Au electrode. X-ray photoelectron spectrum (XPS) of HDT suggests that it forms a monolayer on Au surface through one of the two single bondSH groups and the other single bondSH group is pointing away from the electrode surface. The free single bondSH groups of HDT were used to covalently attach colloidal AuNPs. The covalent attachment of AuNPs on HDT monolayer was confirmed from the observed characteristic carboxylate ion stretching modes of citrate attached with AuNPs in the infra-red reflection absorption spectrum (IRRAS) in addition to a higher reductive desorption charges obtained for AuNPs immobilized on HDT modified Au (Au/HDT/AuNPs) electrode in 0.1 M KOH when compared to HDT modified Au (Au/HDT) electrode. The electron transfer reaction of [Fe(CN)6]4−/3− was markedly hindered at the HDT modified Au (Au/HDT) electrode while it was restored with a peak separation of 74 mV after the immobilization of AuNPs on Au/HDT (Au/HDT/AuNPs) electrode indicating a good electronic communication between the immobilized AuNPs and the underlying bulk Au electrode through a HDT monolayer. The Cottrell slope obtained from the potential-step chronoamperometric measurements for the reduction of ferricyanide at Au/HDT/AuNPs was higher than that of bare Au electrode indicating the increased effective surface area of AuNPs modified electrode. The Au/HDT/AuNPs electrode exhibits excellent electrocatalytic activity towards the oxidation of ascorbic acid (AA) by enhancing the oxidation peak current to more than two times with a 210 mV negative shift in the oxidation potential when compared to a bare Au electrode. The standard heterogeneous electron transfer rate constant (ks) calculated for AA oxidation at Au/HDT/AuNPs electrode was 5.4 × 10−3 cm s−1. The oxidation peak of AA at Au/HDT/AuNPs electrode was highly stable upon repeated potential cycling. Linear calibration plot was obtained for AA over the concentration range of 1–110 μM with a correlation coefficient of 0.9950. The detection limit of AA was found to be 1 μM. The common physiological interferents such as glucose, oxalate ions and urea do not show any interference within the detection limit of AA. The selectivity of the AuNPs modified electrode was illustrated by the determination of AA in the presence of uric acid.

Single atom (Pd/Pt) supported on graphitic carbon nitride as efficient photocatalyst for visible-light reduction of carbon dioxide

Reducing carbon dioxide (CO2) to hydrocarbon fuel with solar energy is significant for high-density solar energy storage and carbon balance. In this work, single palladium/platinum (Pd/Pt) atoms supported on graphitic carbon nitride (g-C3N4), i.e. Pd/g-C3N4 and Pt/g-C3N4, acting as photocatalysts for CO2 reduction were investigated by density function theory (DFT) calcu-lations for the first time. During CO2 reduction, the individual metal atoms function as the active sites, while g-C3N4 provides the source of hydrogen (H*) from hydrogen evolution reaction. The complete, as-designed photocatalysts exhibit excellent activity in CO2 reduction. HCOOH is the preferred product of CO2 reduction on the Pd/g-C3N4 catalyst with a rate-determining barrier of 0.66 eV, while the Pt/g-C3N4 catalyst prefers to reduce CO2 to CH4 with a rate-determining barrier of 1.16 eV. In addition, depositing atom catalysts on g-C3N4 significantly enhances the visible light absorption, rendering them ideal for visible light reduction of CO2. Our findings open a new avenue of CO2 reduction for renewable energy supply.

Polarographic and redox potential studies on copper(I) and copper(II) and their complexes. Part III. Copper (I and II)-ethylene diamine and edta complexes and theory of formation of step reduction waves in cupric copper systems

Polarographic and redox potential measurements on the cupric and cuprous complexes of ethylenediamine and EDTA have been carried out. From the ratio of the stability constants of the cupric and cuprous complexes, and the stability constant of the cupric complex, the stability constant of the cuprous-ethylenediamine complex is obtained. In the case of the EDTA complex it has been possible to obtain only βic/β2ous from the equilibrium concentrations of the cuprous and cupric complexes and the disproportionation constant. The inequalities for the appearance of step reduction waves have been given. The values of the stability constants of the cupric and cuprous complexes determined by the polarographic-redox potential method have been used to explain the appearance of step reduction waves in some systems and the non-appearance in other systems.

Pressure-induced band gap reduction, orientational ordering and reversible amorphization in single crystals of C70: Photoluminescence and Raman studies

Photoluminescence and Raman scattering experiments have been carried out on single crystals of C70 up to 31 GPa to investigate the effect of pressure on the optical band gap, vibrational modes and stability of the molecule. The photoluminescence band shifts to lower energies and the pressure dependence of the band maxima yields the hydrostatic deformation potential to be 2.15 eV. The slope changes in the pressure dependence of peak positions and linewidths of the Raman modes associated with the intramolecular vibrations at 1 GPa mark the known face-centred cubic-->rhombohedral orientational ordering transition. The reversible amorphization in C70 at P > 20 GPa has been compared with the irreversible amorphization in C60 at P > 22 GPa in terms of carbon-carbon distance between the neighbouring molecules at the threshold transition pressures, in conjunction with the interplay between the intermolecular and intramolecular interactions.

Synthesis of single-walled carbon nanotubes using binary (Fe, Co, Ni) alloy nanoparticles prepared in situ by the reduction of oxide solid solutions

Passing a H-2-CH4 mixture over oxide spinels containing two transition elements as in Mg0.8MyMz'Al2O4 (M, M' = Fe, Co or Ni, y + z = 0.2) at 1070 degrees C produces small alloy nanoparticles which enable the formation of carbon nanotubes. Surface area measurements are found to be useful for assessing the yield and quality of the nanotubes. Good-quality single-walled nanotubes (SWNTs) have been obtained in high yields with the FeCo alloy nanoparticles, as evidenced by transmission electron microscope images and surface area measurements. The diameter of the SWNTs is in the 0.8-5 nm range, and the multiwalled nanotubes, found occasionally, possess very few graphite layers. (C) 1999 Elsevier Science B.V. All rights reserved.

Electromagnetic analysis of novel class of multiple core/multiple clad step index single mode optical fiber by analytical means

General propagation properties and universal curves are given for double clad single mode fibers with inner cladding index higher or lower than the outer cladding index, using the parameter: inner cladding/core radii ratio. Mode cut-off conditions are also examined for the cases. It is shown that dispersion properties largely differ from the single clad single mode fiber case, leading to large new possibilities for extension of single mode operation for large wavelength tange. Paper demonstrates that how substantially we can extend the single mode operation range by using the raised inner cladding fiber. Throughout we have applied our own computations technique to find out the eigenvalue for a given modes. Detail derivations with all trivial mathematics for eigenmode equation are derived for each case. Paper also demonstrates that there is not much use of using depressed inner cladding fiber. We have also concluded that using the large inner cladding/inner core radius we can significantly increase the single mode operation range for the large wavelength region. (C) 2015 Elsevier GmbH. All rights reserved.

Step Structure in Cold-Rolled Deformed Nanocrystalline Nickel

The microstructure characteristic of the cold-rolled deformed nanocrystalline nickel metal is studied by transmission electron microscopy. The results show that there are step structures nearby the grain boundary (GB), and the contrast of stress field in front of the step corresponds to the step in the shape. It is indicated that the interaction between twins and dislocations is not a necessary condition to realizing the deformation. In the later stage of the deformation when the grain size becomes about 100nm, the deformation can depend upon the moving of the boundary of the stack faults (SFs) which result from the partial dislocations emitted from GBs. However, when the size of SFs grows up, the local internal stress which is in front of the step gradually becomes higher. When this stress reaches a critical value which stops the gliding of the partial dislocations, the SFs will stop to grow up and leave a step structure behind.

Cold-gas chemical vapor deposition to identify the key precursor for rapidly growing vertically-aligned single-wall and few-wall carbon nanotubes from pyrolyzed ethanol

Vertically-aligned carbon nanotubes (VA-CNTs) were rapidly grown from ethanol and their chemistry has been studied using a "cold-gas" chemical vapor deposition (CVD) method. Ethanol vapor was preheated in a furnace, cooled down and then flowed over cobalt catalysts upon ribbon-shaped substrates at 800 °C, while keeping the gas unheated. CNTs were obtained from ethanol on a sub-micrometer scale without preheating, but on a millimeter scale with preheating at 1000 °C. Acetylene was predicted to be the direct precursor by gas chromatography and gas-phase kinetic simulation, and actually led to millimeter-tall VA-CNTs without preheating when fed with hydrogen and water. There was, however a difference in CNT structure, i.e. mainly few-wall tubes from pyrolyzed ethanol and mainly single-wall tubes for unheated acetylene, and the by-products from ethanol pyrolysis possibly caused this difference. The "cold-gas" CVD, in which the gas-phase and catalytic reactions are separately controlled, allowed us to further understand CNT growth. © 2012 Elsevier Ltd. All rights reserved.

Direct reduction of SO2 to elemental sulfur by the coupling of cold plasma and catalyst (I)

The direct reduction of SO2 to elemental sulfur in flue gas by the coupling of cold plasma and catalyst, being a new approach for SO2 reduction, was studied. In this process, CO2 can be disassembled to form CO, which acts as the reductant under the cold plasma. With the coupling of the cold plasma and the catalyst, sulfur dioxide was selectively reduced by CO to elemental sulfur with a byproduct of metal sulfate, e.g., FeSO4. In the present work, Fe2O3/gamma-Al2O3 was employed as the catalyst. The extent of desulfurization was more than 80%, and the selectivity of elemental sulfur is about 55%. The effects of water vapor, temperature, and the components of simulated flue gas were investigated. At the same time, the coupling of thermogravimetry and infrared method and a chemical analysis method were employed to evaluate the used catalyst. In this paper, we will focus on the discussion of the catalyst. The discussions of the detail of plasma will be introduced in another paper.

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.

Single-crystalline nanowires of SiC synthesized by carbothermal reduction of electrospun PVP/TEOS composite fibres

Nanowires of SiC were synthesized by carbothermally reducing PVP/TEOS composite fibres obtained by electrospinning. High-resolution transmission electron microscopy (HRTEM) and selected-area electron diffraction (SAED) indicated that the SiC nanowires are single crystalline in nature. Both Fourier-transformed infrared spectroscopy and HRTEM indicated that a thin layer of SiO2 was formed on the outer surface of the nanowire as a result of post-heat treatment for the removal of residual carbon. Such SiO2 layer protects the inner SiC fibre from further oxidation. The formation mechanism of single-crystalline SiC nanowires was proposed based on our understanding and characterizations. The growth of the nanowire is believed to be along the ( 111) of its cubic cell.