Mechanisms of Tenebrescence and Persistent Luminescence in Synthetic Hackmanite Na8Al6Si6O24(Cl,S)2.

Synthetic hackmanites, Na8Al6Si6O24(Cl,S)2, showing efficient purple tenebrescence and blue/white persistent luminescence were studied using different spectroscopic techniques to obtain a quantified view on the storage and release of optical energy in these materials. The persistent luminescence emitter was identified as impurity Ti(3+) originating from the precursor materials used in the synthesis, and the energy storage for persistent luminescence was postulated to take place in oxygen vacancies within the aluminosilicate framework. Tenebrescence, on the other hand, was observed to function within the Na4(Cl,S) entities located in the cavities of the aluminosilicate framework. The mechanism of persistent luminescence and tenebrescence in hackmanite is presented for the first time.

In situ FTIR and Raman spectroelectrochemical characterization of graphene oxide upon electrochemical reduction in organic solvents.

Electrochemical reduction of solution cast and self-assembled graphene oxide (GO) films on Au surfaces were studied using organic solvents. During the cyclic voltammetry measurements the structural changes in the films were recorded focusing on in situ infrared and Raman techniques. Both FT-Raman and dispersive Raman spectroscopy were utilized for the reduction studies. The spectroelectrochemical results indicate that the changes in the GO structure take place in a quite narrow potential range extending from -1 to -1.7 V. Higher negative potentials gives rise to reversible changes in the spectra and are not due to reduction processes of GO but more related to changes in the electrolyte media.

Graphene-modified electrode. Determination of hydrogen peroxide at high concentrations.

A gold electrode partially coated by graphene multilayer is developed and tested with respect to high concentrations of hydrogen peroxide. The effective use of conventional electrode materials for the determination of such an analyte by anodic oxidation or cathodic reduction is prevented by the occurrence of adsorptions fouling the electrode surface. This prevents reliable and repeatable voltammetric curves for being recorded and serious problems arise in quantitative analysis via amperometry. The gold-graphene electrode is shown to be effective in quantitative evaluation, by cathodic reduction, of hydrogen peroxide at concentration levels that are of interest in an industrial. Acid, neutral, and basic pH values have been tested through correct adjustment of a Britton Robinson buffer. The experiments have been performed both by cyclic voltammetry and with amperometry at constant potential in unstirred solution. The latter technique has been employed in drawing a calibration linear plot. In particular, the performances of the developed electrode system have been compared with those of both pure gold and pure graphene electrode materials. The bi-component electrode was more sensitive; co-catalytic action by the combination of the two components is hypothesised. The system is stable over many potential cycles, as checked by surface-enhanced Raman spectra recorded over time.

Electrochemical reduction of graphene oxide and its in situ spectroelectrochemical characterization.

The electrochemical properties of self-assembled films of graphene oxide (GO) on mercaptoethylamine (MEA) modified rough Au-surfaces were studied. The film deposition process on MEA primed gold was followed by surface plasmon resonance measurements and the film morphology on 3-aminopropyltriethoxysilane primed Si(100)-surface was studied by atomic force microscopy. The deposited few layer thick GO films on gold were electrochemically reduced by cyclic voltammetry simultaneously as the structural changes in the film were recorded by in situ vibrational spectroscopies. In situ surface enhanced infrared spectroscopy results indicate that the effect of the applied potential on the GO structure could be divided into two parts where the changes occurring at moderate negative potentials are mainly related to changes in the double layer at the film-electrolyte interface and to hydrogen bonding of intercalated water between the GO sheets. At potentials more negative than -0.8 V vs. Ag/AgCl the reduction of GO starts to take place with concomitant conversion of the different functional groups of the film.

Structure of self-assembled multilayers prepared from water-soluble polythiophenes.

We have studied the structure and morphology of self-assembled polyelectrolyte multilayers prepared using poly(styrenesulfonate) (PSS) and four different cationic poly(alkoxythiophene) derivatives bearing methylimidazolium-terminated ionic side chain at the 3-position of the thiophene ring: poly(1-methyl-3-[3-[3-thienyloxy]-propyl]-1H-imidazolium) (P3TOPIM), poly(1-methyl-3-[6-[3-thienyloxy]-hexyl]-1H-imidazolium) (P3TOHIM), poly(1-methyl-3-[2-[(4-methyl-3-thienyl)oxy]-ethyl]-1H-imidazolium ) (P4Me-3TOEIM), and poly(1-methyl-3-[6-[(4-methyl-3-thienyl)oxy]-hexyl]-1H-imidazolium ) (P4Me-3TOHIM). All the multilayers exhibited regular growth. The thickness of the multilayers was measured with ellipsometry, their layer-by-layer growth was followed by polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and ellipsometry, and the morphology of the films was studied by atomic force microscopy (AFM). The length of the methylimidazolium-terminated side chain (C(n), n = 2, 3, 6) and the substituent (H or Me) at the 4-position of the thiophene ring were varied. All multilayers were inhomogeneous in the sub-micrometer scale and contained aggregates of two kinds. The large ones with a low and constant surface number density were attributed to PSS, whereas the small aggregates were polythiophene-based. The surface density of these organic semiconducting nanoparticles greatly depended on the structure of polythiophene, being favored by polymer regioregularity and the length of the side chain. The side chains remained disordered in all the multilayers, but with polythiophenes having hexyl chains both the imidazolium and thiophene rings tended to orient themselves more perpendicular to the surface than in films containing shorter chains (C2 or C3). The relative water content of the multilayers (at 7.1% relative humidity) did not depend on the film thickness and was the lowest for P4Me-3TOHIM. As the number of bilayers increased the methylimidazolium-sulfonate ion pairs gradually weakened and became more individually hydrated.