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Charge Transfer Process (charge + transfer_process)
Selected AbstractsCustomized Electronic Coupling in Self-Assembled Donor,Acceptor NanostructuresADVANCED FUNCTIONAL MATERIALS, Issue 22 2009Dimas G. de Oteyza Abstract Charge transfer processes between donor,acceptor complexes and metallic electrodes are at the heart of novel organic optoelectronic devices such as solar cells. Here, a combined approach of surface-sensitive microscopy, synchrotron radiation spectroscopy, and state-of-the-art ab initio calculations is used to demonstrate the delicate balance that exists between intermolecular and molecule,substrate interactions, hybridization, and charge transfer in model donor,acceptor assemblies at metal-organic interfaces. It is shown that charge transfer and chemical properties of interfaces based on single component layers cannot be naively extrapolated to binary donor,acceptor assemblies. In particular, studying the self-assembly of supramolecular nanostructures on Cu(111), composed of fluorinated copper-phthalocyanines (F16CuPc) and diindenoperylene (DIP), it is found that, in reference to the associated single component layers, the donor (DIP) decouples electronically from the metal surface, while the acceptor (F16CuPc) suffers strong hybridization with the substrate. [source] Charge transfer processes in cyano-bridged transition metalsPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 1 2009Hayato Kamioka Abstract We have applied a time-resolved absorption spectroscopy to investigate the charge transfer (CT) processes in the Prussian Blue-type cyanides MII[FeIII(CN)6]0.675H2O (M = Mn, Co) embedded in a Nafion film. In the Mn-Fe cyanide, we observed the bleaching of the CT band at 2.4 eV, similar to that found in the Co-Fe cyanide. We found that the lifetime of the photo-induced CT state in Mn-Fe cyanide shows significant dependence on the excitation photon energy. This is in sharp contrast to the case of the Co-Fe cyanide. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Alternative Mechanistic Paths in the Hetero-Diels,Alder Reaction of ,-Oxothiones: A Theoretical StudyEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 21 2007Laura Legnani Abstract DFT calculations at the B3LYP/6-311+G(d,p) level for the C, H, and O atoms and at the 6-311+G(2df,p) level for the S atom were used to study the hetero-Diels,Alder reactions between several ,-oxothiones and ethylene or methyl vinyl ether (MVE). All the transition states and the intermediates along the reaction pathways, as well as the reaction products, were located. The reactions with ethylene are all concerted though asynchronous whereas in the reactions with MVE the electron-releasing character of the methoxy substituent lowers the energy barriers and enhances the asynchronicity and the charge transfer process to such an extent that the reaction may become unconcerted and exhibit a two-step mechanism with a zwitterionic intermediate derived from nucleophilic attack of electron-rich MVE to the sulfur atom of the strongly electrophilically activated ,-oxothiones. The reactions are also favored by the conjugation of the newly formed C=C bond. Moreover, the geometric features of the diene exert a nonnegligible role, as dienes that are planar or almost planar in their ground state show a lower energy barrier. Thus, both geometric and electronic features of the dienes as well as of the dienophiles play a significant role in the easiness of the reactions and in their mechanism. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Evaluation of RuxWySez Catalyst as a Cathode Electrode in a Polymer Electrolyte Membrane Fuel CellFUEL CELLS, Issue 1 2010K. Suárez-Alcántara Abstract The oxygen reduction reaction (ORR) on RuxWySez is of great importance in the development of a novel cathode electrode in a polymer electrolyte membrane fuel cell (PEMFC) technology. The RuxWySez electrocatalyst was synthesised in an organic solvent for 3,h. The powder was characterised by transmission electron microscopy (TEM), and powder X-ray diffraction (XRD). The electrocatalyst consisted of agglomerates of nanometric size (,50,150,nm) particles. In the electrochemical studies, rotating disc electrode (RDE) and rotating ring-disc electrode (RRDE) techniques were used to determine the oxygen reduction kinetics in 0.5,M H2SO4. The kinetic studies include the determination of Tafel slope (112,mV,dec,1), exchange current density at 25,°C (1.48,×,10,4,mA,cm,2) and the apparent activation energy of the oxygen reaction (52.1,,,0.4,kJ,mol,1). Analysis of the data shows a multi-electron charge transfer process to water formation, with 2% H2O2 production. A single PEMFC with the RuxWySez cathode catalysts generated a power density of 180,mW,cm,2. Performance achieved with a loading of 1.4,mg,cm,2 of a 40,wt% RuxWySez and 60,wt% carbon Vulcan (i.e. 0.56,mg,cm,2 of pure RuxWySez). Single PEMFC working was obtained with hydrogen and oxygen at 80,°C with 30,psi. [source] The Role of the Oxygen/Water Redox Couple in Suppressing Electron Conduction in Field-Effect TransistorsADVANCED MATERIALS, Issue 30 2009Carla M. Aguirre The suppression of electron (n-type) conduction observed in back-gated field effect transistors is the result of an electrochemical charge transfer process to the oxygen/water layer adsorbed on hydrophilic substrates. The impact of this phenomenon is demonstrated with nanoscale and thin-film carbon nanotube transistors. [source] Potential Modulated Attenuated Total Reflectance Spectroscopy of Prussian Blue Films on ITOISRAEL JOURNAL OF CHEMISTRY, Issue 3 2006Zeynep Ozkan Araci Potential modulated attenuated total reflectance (PM-ATR) spectroscopy has been employed to study charge transfer processes in Prussian blue (PB) films deposited on indium tin oxide (ITO) electrodes. PM-ATR is a planar waveguide-based spectroelectrochemical technique in which the optical response of an electroactive film is measured as a function of applied potential and modulation frequency. The multiple internal reflection geometry of PM-ATR provides a significant sensitivity advantage over the single external reflectance geometry that has been employed in most prior electroreflectance studies. The apparent electron transfer rate of PB on ITO obtained using PM-ATR was compared to that obtained with conventional cyclic voltammetry; the respective rates, 0.33 ± 0.15 s,1 (n = 3) and 0.71 ± 0.37 s,1 (n = 10), are in good agreement. [source] Photoreactions of 1,4-Naphthoquinones: Effects of Substituents and Water on the Intermediates and Reactivity,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 2 2005Helmut Görner ABSTRACT The photochemistry of lapachol and other 1,4-naphthoquinone (NQ) derivatives, e.g. 2-methoxy-1,4-naphthoquinone (MeONQ), 2-hydroxy-1,4-naphthoquinone (2-HONQ) or 5-hydroxy-1,4-naphthoquinone (5-HONQ) and 2-methyl-5-hydroxy-1,4-naphthoquinone (P-NQ) in solution at room temperature was studied by ultraviolet-visible spectroscopy after nanosecond laser pulses at 248 nm. The triplet state and semiquinone radicals were observed for MeONQ, HONQ and P-NQ, whereas for lapachol, intramolecular H-atom and charge transfer processes take place, as in the case of vitamin K1. The photoinduced reaction of NQ into HONQ is initiated by nucleophilic water addition to the triplet state, and for the secondary reactions, a modified mechanism is proposed. [source] Impedance spectroscopy as a tool for non-intrusive detection of extracellular mediators in microbial fuel cellsBIOTECHNOLOGY & BIOENGINEERING, Issue 5 2009Ramaraja P. Ramasamy Abstract Endogenously produced, diffusible redox mediators can act as electron shuttles for bacterial respiration. Accordingly, the mediators also serve a critical role in microbial fuel cells (MFCs), as they assist extracellular electron transfer from the bacteria to the anode serving as the intermediate electron sink. Electrochemical impedance spectroscopy (EIS) may be a valuable tool for evaluating the role of mediators in an operating MFC. EIS offers distinct advantages over some conventional analytical methods for the investigation of MFC systems because EIS can elucidate the electrochemical properties of various charge transfer processes in the bio-energetic pathway. Preliminary investigations of Shewanella oneidensis DSP10-based MFCs revealved that even low quantities of extracellular mediators significantly influence the impedance behavior of MFCs. EIS results also suggested that for the model MFC studied, electron transfer from the mediator to the anode may be up to 15 times faster than the electron transfer from bacteria to the mediator. When a simple carbonate membrane separated the anode and cathode chambers, the extracellular mediators were also detected at the cathode, indicating diffusion from the anode under open circuit conditions. The findings demonstrated that EIS can be used as a tool to indicate presence of extracellular redox mediators produced by microorganisms and their participation in extracellular electron shuttling. Biotechnol. Bioeng. 2009; 104: 882,891. © 2009 Wiley Periodicals, Inc. [source] | ||||||||||||||||