Dye Bonding to TiO(2): In Situ Attenuated Total Reflection Infrared Spectroscopy Study, Simulations, and Correlation with Dye-Sensitized Solar Cell Characteristics

Processing dye-sensitized solar cells gains more and more importance as interest in industrial applications grows daily. For large-scale processing and optimizing manufacturing in terms of environmental acceptability as well as time and material saving, a detailed knowledge of certain process steps is crucial. In this paper we concentrate on the sensitizing step of production, i.e., the anchoring of the dye molecules onto the TiO(2) semiconductor. A vacuum-tight attentuated total reflection infrared (ATR-IR) flow-through cell was developed, thus allowing measurements using a vacuum spectrometer to monitor infiltration of dye molecules into the porous TiO(2) film in situ at high sensitivity. In particular, the influence of the anchor and backbone of perylene dye molecules as well as the influence of solvents on the adsorption process was investigated. The experiments clearly show that an anhydride group reacts much slower than an acid group. A significantly lower amount of anhydride dye can be adsorbed on the films. Ex situ transmission experiments furthermore indicate that the availability of OH groups on the TiO(2) surface may limit dye adsorption. Also the backbone and base frame of the dye can influence the adsorption time drastically. Electrical cell characteristics correlate with the amount of adsorbed dye molecules determined by in situ ATR-IR measurements. The latter is also sensitive toward the diffusion of the dye through the porous layer. To gain a deeper understanding of the interplay between diffusion and adsorption, simulations were performed that allowed us to extract diffusion and adsorption constants. Again it was demonstrated that the anchoring group has a strong effect on the adsorption rate. The influence of the solvent was also studied, and it was found that both adsorption and desorption are affected by the solvent. Protic polar solvents are able to remove bound dye molecules, which is a possible pathway of cell degradation. Most importantly, the analysis shows the potential of this approach for the evaluation of molecules or additives concerning their characteristics important for cell processing.     

Effect of gamma radiation on the physico-chemical properties of alginate-based films and beads

Alginate solution (3%, w/v) was prepared using deionized water from its powder. Then the solution was exposed to gamma radiation (0.1?25 kGy). The alginate films were prepared by solution casting. It was found that gamma radiation has strong effect on alginate solution. At low doses, mechanical strength of the alginate films improved but after 5 kGy dose, the strength started to decrease. The mechanism of alginate radiolysis in aqueous solution is discussed. Film formation was not possible from alginate solution at doses >5 kGy. The mechanical properties such as puncture strength (PS), puncture deformation (PD), viscoelasticity (Y) coefficient of the un-irradiated films were investigated. The values of PS, PD and Y coefficient of the films were 333 N/mm, 3.20 mm and 27%, respectively. Alginate beads were prepared from 3% alginate solution (w/v) by ionotropic gelation method in 5% CaCl₂ solution. The rate of gel swelling improved in irradiated alginate-based beads at low doses (up to 0.5 kGy).     

Suicide inhibition of alpha-oxamine synthases: structures of the covalent adducts of 8-amino-7-oxononanoate synthase with trifluoroalanine

The irreversible inhibition of 8-amino-7-oxononanoate synthase by trifluoroalanine involves decarboxylative defluorination of the inhibitor-PLP aldimine followed by attack of the conjugated imine by the amino group of the active site lysine to afford a covalently bound difluorinated intermediate which can subsequently undergo further HF losses and hydrolysis to afford a 2-(pyridoximine phosphate) acetoyl protein adduct.     

Efficient visible light-active N-doped TiO2 photocatalysts by a reproducible and controllable synthetic route

A reproducible and controllable method allows the synthesis of practical quantities of efficient, visible light active TiO(2)(N) photocatalysts in which the nitrogen content may be varied to achieve optimum performance.     

FTIR, FT-Raman spectra and ab initio DFT vibrational analysis of 2-amino-5-chloropyridine

The FTIR and FT-Raman spectra of 2-amino-5-chloropyridine (ACP) has been recorded in the region 4000-400 and 3500-100 cm-1, respectively. The optimized geometry, frequency and intensity of the vibrational bands of ACP were obtained by the ab initio and density functional theory (DFT) levels of theory with complete relaxation in the potential energy surface using 6-31G(d,p) and 6-311+G(2df,2p) basis sets. The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental FTIR and FT-Raman spectra. The observed and the calculated frequencies are found to be in good agreement. The experimental spectra also coincide satisfactorily with those of theoretically constructed bar type spectrograms.     

Microemulsions.Background,New Concepts,Applications, Perspectives. Edited by Cosima Stubenrauch.

John Wiley & Sons, Hoboken 2008. 400 pp., hardcover € 129.00.—ISBN 978‐1405167826

     

The capillary interaction between two vertical cylinders

Particles floating at the surface of a liquid generally deform the liquid surface. Minimizing the energetic cost of these deformations results in an inter-particle force which is usually attractive and causes floating particles to aggregate and form surface clusters. Here we present a numerical method for determining the three-dimensional meniscus around a pair of vertical circular cylinders. This involves the numerical solution of the fully nonlinear Laplace-Young equation using a mesh-free finite difference method. Inter-particle force-separation curves for pairs of vertical cylinders are then calculated for different radii and contact angles. These results are compared with previously published asymptotic and experimental results. For large inter-particle separations and conditions such that the meniscus slope remains small everywhere, good agreement is found between all three approaches (numerical, asymptotic and experimental). This is as expected since the asymptotic results were derived using the linearized Laplace-Young equation. For steeper menisci and smaller inter-particle separations, however, the numerical simulation resolves discrepancies between existing asymptotic and experimental results, demonstrating that this discrepancy was due to the nonlinearity of the Laplace-Young equation.     

New regularity theorems for non-autonomous variational integrals with (p, q)-growth

One prominent problem in the calculus of variations is minimizing anisotropic integrals with a (p, q)-elliptic density F depending on the gradient of a function ${w : \Omega \rightarrow \mathbb{R}^N}$ with ${\Omega \subset \mathbb{R}^n}$ . The best known sufficient bound for regularity of solutions is q <?p (n?+?2)/n. On the other hand, if we allow an additional x-dependence of the density we have the much weaker result q <?p (n + 1)/n. If one additionally imposes the local boundedness of the minimizer, then these bounds can be improved to q <?p?+?2 and q <?p?+?1. In this paper we give natural assumptions for F closing the gap between the autonomous and non-autonomous situation.     

Single-Ion Conducting Polymer Electrolyte for Superior Sodium-Metal Batteries

Sodium-metal batteries (SMBs) are considered a potential alternative to high-energy lithium-metal batteries (LMBs). However, the high reactivity of metallic sodium towards common liquid organic electrolytes renders such battery technology particularly challenging. Herein, we propose a multi-block single-ion conducting polymer electrolyte (SIPE) doped with ethylene carbonate as suitable electrolyte system for SMBs. This novel SIPE provides a very high ionic conductivity (2.6 mS cm⁻¹) and an electrochemical stability window of about 4.1 V at 40 °C, enabling stable sodium stripping and plating and excellent rate capability of Na||Na₃V₂(PO₄)₃ cells up to 2 C. Remarkably, such cells provide a capacity retention of about 85 % after 1,000 cycles at 0.2 C thanks to the very high Coulombic efficiency (99.9 %), resulting from an excellent interfacial stability towards sodium metal and the Na₃V₂(PO₄)₃ cathode.