Kinetic Limitations (kinetic + limitation)

Distribution by Scientific Domains

Selected Abstracts

Overcoming Kinetic Limitations of Electron Injection in the Dye Solar Cell via Coadsorption and FRET

CHEMPHYSCHEM, Issue 5 2008
Conrad Siegers
Abstract A new, extremely simple concept for the use of energy transfer as a means to the enhancement of light absorption and current generation in the dye solar cell (DSC) is presented. This model study is based upon a carboxy-functionalized 4-aminonaphthalimide dye (carboxy-fluorol) as donor, and (NBu4)2[Ru(dcbpy)2(NCS)2] (N719) as acceptor chromophores. A set of three different devices is assembled containing either exclusively carboxy-fluorol or N719, or a mixture of both. This set of transparent devices is characterized via IV-measurements under AM1.5G and monochromatic illumination and their light-harvesting and external quantum efficiencies (LHE and EQE, respectively) are determined as well. It is shown that the device containing only the donor chromophore has a marginal power conversion efficiency, thus indicating that carboxy-fluorol is a poor sensitizer for the DSC. Cyclovoltametric measurements show that the poor sensitization ability arises from the kinetic inhibition of electron injection into the TiO2 conduction band. Comparing the spectral properties of the DSCs assembled presently, however, demonstrates that light absorbed by carboxy-fluorol is almost quantitatively contributing to the photocurrent if N719 is present as an additional sensitizer. In this case, N719 acts as a catalyst for the sensitization of TiO2 by carboxy-fluorol in addition to being a photosensitizer. Evaluation of the maximum output power under blue illumination shows that the introduction of an energy-donor moiety via coadsorption, leads to a significant increase in the monochromatic maximum output power. This result demonstrates that energy transfer between coadsorbed chromophores could be useful for the generation of current in dye-sensitized solar cells. [source]

Kinetic limitations of a bioelectrochemical electrode using carbon nanotube-attached glucose oxidase for biofuel cells

Xueyan Zhao
Abstract Carbon nanotubes (CNTs) have been used for various bioelectrochemical applications, presumably for substantial improvement in performance. However, often only moderate results observed, with many governing factors have been considered and suggested yet without much systematic evaluation and verification. In this study, CNT-supported glucose oxidase (CNT,GOx) was examined in the presence of 1,4-benzoquinone (BQ). The intrinsic Michaelis parameters of the reaction catalyzed by CNT,GOx were found very close to those of native GOx. However, the Nafion entrapment of CNT,GOx for an electrode resulted in a much lower activity due to the limited availability of the embedded enzyme. Interestingly, kinetic studies revealed that the biofuel cell employing such an enzyme electrode only generated a power density equivalent to <40% of the reaction capability of the enzyme on electrode. It appeared to us that factors such as electron and proton transfer resistances can be more overwhelming than the heterogeneous reaction kinetics in limiting the power generation of such biofuel cells. Biotechnol. Bioeng. 2009; 104: 1068,1074. © 2009 Wiley Periodicals, Inc. [source]

Electrochemical Reduction of S(IV) Compounds in Water-Ethanol Solutions at Nafion/Tetraruthenated Porphyrins Glassy Carbon Modified Electrodes

Karla Calfumán
Abstract This work describes electrocatalytic detection of S(IV) compounds in water-ethanol solutions under acidic conditions, on a glassy carbon electrode modified with Co(II) tetraruthenated porphyrin electrostatically assembled onto a Nafion film. The Ipc current shows a linear relationship with the concentration of S(IV) oxo-anions. Controlled potential electrolysis shows that thiosulfate was detected as reaction product. Rotating disk electrode and UV-visible spectroelectrochemistry experiments showed a kinetic limitation to the electron transfer controlled by charge propagation in the film and the formation of an intermediary between Co center and S(IV) species. The reproducibility of the modification methodology presents a RSD of 4.1%. [source]

Metabolic control analysis of an enzymatic biofuel cell

Doris J. Glykys
Abstract Metabolic control analysis (MCA) is an analytical technique that aims to quantify the distribution of control that enzymes exhibit over the steady-state fluxes through a metabolic network. In an enzymatic biofuel cell, the flux of interest is the electrical current generated by the system. Regardless of transport limitations and other constraints, kinetic limitations can become potential bottlenecks in the operation of a biofuel cell. We have used an indirect approach to MCA to investigate a common osmium-mediated glucose oxidase/laccase enzymatic biofuel cell. The results of the analysis show that the control of the electron flux strongly depends on the total mediator concentrations and the extent of polarization of the individual electrodes. The effect of varying oxygen concentrations is also examined, as oxygen is required for the cathode, but it participates in a non-productive reaction at the anode. Under normal operating conditions the electrodes will be highly polarized and will both contain high mediator concentrations. This configuration will result in a dominant FCC at the anode, and the conditions that are needed for balanced flux control between the anode and cathode are explored. As increasingly complex bioelectrocatalytic systems and architectures are envisioned, MCA will be a valuable framework to facilitate their design and subsequent operation. Biotechnol. Bioeng. 2009;102: 1624,1635. © 2008 Wiley Periodicals, Inc. [source]