Correlation of vibrational intensity with fluorescence lifetimes in π conjugated polymers

A series of novel pi (π) conjugated polymers, originating from the archetypical Polyphenylene vinylene, in which the phenyl units are successively replaced by the larger naphthyl and anthryl acene units, were previously found to have a well-defined relationship between their relative fluorescence yields and their vibrational characteristics, as determined by Raman spectroscopy. In this study the Strickler-Berg equation is used to probe the influence of continual substitution of higher order acene units into the conjugated backbone in terms of the variation of the radiative and non-radiative rates. The deconvolution of the radiative and non-radiative rates enables the correlation of the reduction of the Raman intensity and concomitant increase in the fluorescence yield with the reduction of the non-radiative rate. This confirms that the reduction of the non-radiative rate is the dominant process introduced by the vibrational confinement originating from systematic substitution of higher order acene units into the polymer backbone.     

铒氨基酸固态配合物的光声光谱研究

合成了Er(Gly)3Cl3·3H2O、Er(Ala)3Cl3·3H2O和Er(Gly)3Phen·3H2O二元及三元固态配合物微晶粉末,在300nm～800nm范围内测定并解释了其光声光谱。通过对光声相对强度计算得到铒氨基酸固态配合物的光声支量,讨论了氨基酸配体对中心稀土离子铒f-f跃迁的微扰作用。结合Er(Ala)3Cl3·3H2O配合物的光声光谱和吸收光谱研究了其荧光性质及弛豫模型。     

Electron spectroscopies and their use for materials characterization

We present here a general overview of electron spectroscopies from a practical point of view. The most frequently used ones are described and the type of structural information they can provide on materials is explained in relation to the physical processes on which they are based. Furthermore, we explore critically and in detail various tools that have been developed to allow a systematic solving of structures by these spectroscopies.     

Reversible changes of the fill factor in the ZnO/CdS/Cu(In,Ga)Se2 solar cells

The reversible persistent changes of the fill factor (FF) induced by the illumination and voltage bias along with changes in the electronic properties of the ZnO/CdS/Cu(In,Ga)Se₂ photovoltaic devices have been studied. Admittance spectroscopy and capacitance–voltage characterization reveal a correlation between the FF and the space charge distribution within the absorber. Our experiments provide evidence that a major source of FF loss in efficient devices is caused by excess negative charge close to the interface. We explain the persistent changes in the net acceptor concentration in the interface region by the relaxation effects due to compensating donors—the same mechanism, which leads to metastable changes of the doping level in the bulk of the absorber.     

Oxidation of oleuropein studied by EPR and spectrophotometry

The autoxidation at alkaline pH and enzymatic oxidation by mushroom tyrosinase of oleuropein, the dominant biophenol present in the fruits and leaves of Olea europea, was followed by both electron paramagnetic resonance (EPR) and absorption spectroscopy. For comparison, the same oxidation processes were applied to 4‐methylcatechol, a simple polyphenol present in olive mill wastewaters. EPR spectra of stable o‐semiquinone radicals produced during autoxidation at pH 12 and short‐lived o‐semiquinone free radicals produced during autoxidation at pH 9.0 or tyrosinase action and stabilized by chelation with a diamagnetic metal ion (Mg²⁺) were recorded for both polyphenols, and the corresponding hyperfine splitting constants were determined. The UV‐Vis spectral characteristics of the oxidation of polyphenols were highly dependent on the type of polyphenol, oxidant type and the pH of the reaction. The kinetic behavior of tyrosinase in the presence of oleuropein and 4‐methylcatechol was followed by recording spectral changes at 400 nm (absorption maximum) over time. The tysosinase activity with oleuropein showed a pronounced pH optimum at pH 6.5 and a minor one around pH 8. From the data analysis of the initial rate at pH 6.5, the kinetic parameters K_m = 0.34 ± 0.03 mM and V_max = 0.029 ± 0.002 ΔA₄₀₀ min^–1 were determined for oleuropein.     

反应温度对聚苯胺薄膜生长的影响

在不同反应温度条件下采用原位聚合法在石英基片上制备了聚苯胺薄膜．对薄膜样品进行了紫外光谱、SEM、电性能表征。实验结果表明，过高的合成温度会加速聚合反应过程，抑制膜厚的增长，引起薄膜的热降解，进而对样品的导电性产生不良影响。根据生长速率与合成温度的依赖关系，估算了聚合反应的活化能Ea=34.4kJ/mol。     

Streaming potential measurements on stainless steels surfaces: evidence of a gel-like layer at the steel/electrolyte interface

Electric charges at the surface of a passive stainless steel are generally considered as concentrated either in the passive film itself, or at the metal/passive film interface, or in the electrical double layer at the film solution interface. Rest potential time dependence after immersion of a passive surface in aqueous electrolytes suggests however that slow processes occur in the onset of the surface charge. Specific experiments, such as streaming potential measurements and electrochemical impedance spectroscopy in a thin electrolyte cell, were carried out for understanding better this phenomenon. An AISI 304 type austenitic stainless steel with polished or bright annealed surface finishes was immersed in NaCl aqueous solutions with various pH and chloride concentrations. The streaming potential time evolution shows two steps: a first rapid one (∼2 min) is attributed to the onset of the surface charge. The second step is much slower (approximately several hours) and possibly due to an interphase layer between the passive film and the solution. Following this idea, the whole kinetics is controlled by cation migration across the interphase when the pH is larger than the isoelectric pH (pH_iep), while chloride ions are incorporated in the interphase when pH < pH_iep. Impedance measurements allow determining both the kinetics of charge transport and the thin cell conductivity. When glass is used as reference material for the cell walls instead of stainless steel, the Nyquist plots show a high-frequency response. For stainless steel cell walls, a low-frequency response is observed, attributed to a slow charge reorganisation inside the interphase layer. The charge distribution at metal/electrolyte interface is discussed in terms of a gel-like layer which possibly takes place at the passive film/electrolyte interface.     

Spatially resolved infrared spectroscopy: a novel technique for in situ study of spatial surface coverage during CO oxidation on supported catalysts

A spatially resolved infrared (IR) imaging technique to monitor the linear adsorbed CO coverage on supported catalyst surface combining an IR bandpass filter and an IR thermography camera has been developed. Images acquired during the CO adsorption/desorption and ignition indicate that the technique provides an excellent method to image the change of surface coverage with a spatial resolution. It is expected that the combination of infrared thermography with spatially resolved imaging of surface coverage will provide a deeper insight in the dynamics of spatio-temporal patterns on heterogeneous catalysts.     

Methanol adsorption and dehydration on alkali metal exchanged NaY zeolites

FT-IR spectroscopy has been applied in a study of methanol adsorption on M^INaY zeolites (M=Li, K, Rb, Cs). Coordinatively and/or hydrogen bonded methanol was registered in the temperature range 300–473 K. Dehydration of methanol to dimethyl ether occurred at 573 and 623 K. It was found that the activity of the catalyst for methanol dehydration strongly depends on the kind of alkali metal cation, and well correlates the IR data relative to methanol adsorption.