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Selected AbstractsBioelectrocatalysis of Oxygen Reduction Reaction by Laccase on Gold ElectrodesELECTROANALYSIS, Issue 13-14 2004Gautam Gupta Abstract Direct electron transfer (DET) reaction of oxygen electroreduction catalyzed by enzyme laccase on monolayer modified gold electrodes was studied. Three different monolayers were investigated, from which 4-aminothiophenol was found to be optimal for the direct electron transfer to take place. The electrocatalytic reduction of the oxygen at the electrode surface was found to depend significantly on the method of immobilization. Fungal laccase from Coriolus hirsitus modified with sodium-periodate demonstrated more anodic onset potential for oxygen reduction than the tree laccase from Rhus vernicifera. Physical immobilization of enzyme did not result in any manifestation of bioelectrocatalytic activity. A maximum anodic shift in reduction potential of 300,mV was observed for fungal laccase covalently coupled on the electrode surface. [source] Controlling Photoactivity in Ultrathin Hematite Films for Solar Water-SplittingADVANCED FUNCTIONAL MATERIALS, Issue 7 2010Florian Le Formal Abstract A promising route to increase the performance of hematite (,-Fe2O3) photoelectrodes for solar hydrogen production through water-splitting is to use an extremely thin layer of this visible light absorber on a nanostructured scaffold. However, the typically poor performance of ultrathin (ca. 20,nm) films of hematite has been the limiting factor in implementing this approach. Here, the surprising effect of a substrate pretreatment using tetraethoxysilicate (TEOS) is reported; it results in drastic improvements in the photoperformance of 12.5,nm thick films of hematite. These films exhibit a water oxidation photocurrent onset potential at 1.1,V versus the reversible hydrogen electrode (vs. RHE) and a plateau current of 0.63,mA cm,2 at 1.5,V vs. RHE under standard illumination conditions, representing the highest reported performance for ultrathin hematite films. In contrast, almost no photoactivity is observed for the photoanode with the same amount of hematite on an untreated substrate. A detailed study of the effects of the TEOS treatment shows that a monolayer of SiOx is formed, which acts to change the hematite nucleation and growth mechanism, increases its crystallinity, reduces the concentration of carrier trapping states of the ultrathin films, and suggests its further application to quantum-dot and extremely-thin-absorber (ETA)-type solar cells. [source] Synthesis, photoluminescence, and electrochromic properties of wholly aromatic polyamides bearing naphthylamine chromophoresJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 20 2006Guey-Sheng Liou Abstract A series of novel polyamides with pendent naphthylamine units having inherent viscosities of 0.15,1.02 dL/g were prepared via direct phosphorylation polycondensation from various diamines and a naphthylamine-based aromatic dicarboxylic acid, 1-[N,N -di(4-carboxyphenyl)amino]naphthalene. These amorphous polyamides were readily soluble in various organic solvents and could be cast into transparent and tough films. The aromatic polyamides had useful levels of thermal stability associated with high glass-transition temperatures (268,355 °C), 10% weight loss temperatures in excess of 480 °C, and char yields at 800 °C in nitrogen higher than 60%. These polymers showed maximum ultraviolet,visible absorption at 350,358 nm and exhibited fluorescence emission maxima around 435,458 nm in N -methyl-2-pyrrolidinone solutions with fluorescence quantum yields ranging from 0.4 to 15.0%. The hole-transporting and electrochromic properties were examined with electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the polyamide films cast onto an indium tin oxide coated glass substrate exhibited one oxidative redox couple around 1.08,1.16 V (oxidation onset potential) versus Ag/AgCl in an acetonitrile solution and revealed good stability of the electrochromic characteristics, with a color change from colorless to green at applied potentials ranging from 0 to 1.6 V. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6094,6102, 2006 [source] Photoelectrochemical Behavior of Nanostructured WO3 Thin-Film Electrodes: The Oxidation of Formic AcidCHEMPHYSCHEM, Issue 12 2006Damián Monllor-Satoca Abstract Nanostructured tungsten trioxide thin-film electrodes are prepared on conducting glass substrates by either potentiostatic electrodeposition from aqueous solutions of peroxotungstic acid or direct deposition of WO3 slurries. Once treated thermally in air at 450,°C, the electrodes are found to be composed of monoclinic WO3 grains with a particle size around 30,40 nm. The photoelectrochemical behavior of these electrodes in 1,M HClO4 apparently reveals a low degree of electron,hole recombination. Upon addition of formic acid, the electrode showed the current multiplication phenomenon together with a shift of the photocurrent onset potential toward less positive values. Photoelectrochemical experiments devised on the basis of a kinetic model reported recently [I. Mora-Seró, T. Lana-Villarreal, J. Bisquert, A. Pitarch, R. Gómez, P. Salvador, J. Phys. Chem. B2005, 109, 3371] showed that an interfacial mechanism of inelastic, direct hole transfer takes place in the photooxidation of formic acid. This behavior is attributed to the tendency of formic acid molecules to be specifically adsorbed on the WO3 nanoparticles, as evidenced by attenuated total reflection infrared spectroscopy. [source] Synthesis and properties of nitrogen-linked poly(2,7-carbazole)s as hole-transport material for organic light emitting diodesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2009Tsuyoshi Michinobu Abstract A novel class of carbazole polymers, nitrogen-linked poly(2,7-carbazole)s, was synthesized by polycondensation between two bifunctional monomers using the palladium-catalyzed amination reaction. The polymers were characterized by 1H NMR, Infrared, Gel permeation chromatography, and MALDI-TOF MS and it was revealed that the combination of the monomer structures is important for producing high molecular weight polymers. Thermal analysis indicated a good thermal stability with high glass transition temperatures, e.g., 138 °C for the higher molecular weight polymer P2. To pursue the application possibilities of these polymers, their optical properties and energy levels were investigated by UV-Vis absorption and fluorescence spectra as well as their electrochemical characteristics. Although the blue light emission was indeed observed for all polymers in solution, the quantum yields were very low and the solid films were not fluorescent. On the other hand, the HOMO levels of the polymers estimated from the onset potentials for the first oxidation in the solid thin films were relatively high in the range of ,5.12 to ,5.20 eV. Therefore, light emitting diodes employing these polymers as a hole-transport layer and iridium(III) complex as a triplet emitter were fabricated. The device of the nitrogen-linked poly(2,7-carbazole) P3 with p,p,-biphenyl spacer, which has a higher HOMO level and a higher molecular weight, showed a much better performance than the device of P2 with m -phenylene spacer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3880,3891, 2009 [source] |