Catalytic steam gasification of Miscanthus X giganteus in fluidised bed reactor on olivine based catalysts

The Miscanthus X giganteus (MXG) presents many advantages (high yield, perennial crop, easy harvesting…) so it can be considered as a good candidate in terms of renewable energy sources. Several works have been carried out and were devoted to the MXG, especially in the agricultural field, but this study is the first which deals with gasification in order to produce syngas. The catalytic steam gasification of MXG in a fluidised bed reactor into presence of olivine based catalysts was investigated. Three parameters were studied, the temperature (800 °C and 900 °C), the pellets size (6 mm and 8 mm) and the nature of catalyst (olivine and Ni/olivine). Noteworthy is the efficiency shown by the Ni/olivine at 800 °C, which leads to the production of 1.7 m³ kg^− 1 daf of gas, containing 50% of H₂. Ni/olivine catalyst was characterised by XRD, TPR and SEM-EDX in order to monitor its structural changes during the process. Moreover, a solvent system of tar recovery was tested, which allows to obtain a more representative set of the whole tars. Then, the tars composition was determined by GC/MS. The identification of different compounds shows the presence of different PAHs, in majority naphthalene.     

Access to new carbohydrate-functionalized polylactides via organocatalyzed ring-opening polymerization

The 4-dimethylaminopyridine (DMAP) catalyzed ring-opening polymerization of lactide using various carbohydrate initiators has been assessed for the functionalization of polylactide. Selectively protected glucose derivatives bearing a free primary alcohol (Glc-1r) and a free secondary alcohol (Glc-2r), glucose and cyclodextrin diol derivatives (Glc-diol and CD-diol), methyl-α-d-glucopyranoside (Glc-Me) and native β-cyclodextrin (CD) were used as initiators. According to the solubility of the carbohydrate derivative, the polymerizations were conducted in chlorinated solvents and in the bulk. Relatively narrow distributions are obtained in high yields in the absence of side reactions, affording a 100% functionalization efficiency. The catalytic synthesis of new carbohydrate link-functionalized polylactides and carbohydrate core star polylactides is reported.     

Insight into β-Carotene Thermal Degradation in Oils with Multiresponse Modeling

The aim of this study was to gain further insight into β-carotene thermal degradation in oils. Multiresponse modeling was applied to experimental high-performance liquid chromatography–diode array detection (HPLC–DAD) data (trans-, 13-cis-, and 9-cis-β-carotene concentrations) during the heat treatments (120–180 °C) of two β-carotene-enriched oils, i.e., palm olein and copra. The test of different reaction schemes showed that β-carotene isomerization reactions were dominant and reversible. The resulting cis isomers and trans-β-carotene simultaneously underwent oxidation and cleavage reactions at the same rate constant. From the kinetic analysis, it appeared that—contrary to oxidation and cleavage reactions—isomerization rate constants did not follow the Arrhenius law. However, the isomerization equilibrium constant increased with temperature, favoring isomer production, particularly 9-cis-β-carotene. Its production was shown to be concomitant with oxidation and cleavage reactions, indicating that 9-cis-β-carotene could be a good degradation indicator during oil storage or processing.     

Mechanism of formation of urchin-like ZnO

Thin films composed of ZnO nanowires (NWs) hierarchically organized with an urchin-like 3D morphology were obtained by combining the electrochemical deposition and sphere lithography methods. Deposited on a transparent conductive oxide substrate (TCO), a monolayer of carboxylate modified polystyrene spheres organized with a hexagonal closed-packed structure played the role of a template. The spheres were activated in a solution of zinc chloride by the formation of bonds between the carboxylate terminals and the Zn²⁺ ions and were used as a template for the electrodeposition of vertically aligned ZnO NWs around them. Without this treatment, ZnO NWs were deposited only on the TCO substrate between the PS spheres. To reach a density of nanowires high enough to obtain the urchin morphology, the concentration of ZnCl₂ had to be at least equal to 2 M. It was also found, as soon as small grains of ZnO started to be electrodeposited on the polystyrene spheres that the spheres were no longer close packed. The space created between them increased with the increase in the number of small ZnO grains and the increase in their length, allowing the further growth of the nanowires between the spheres. As a result the initial round shape of the spheres was modified and the urchin-like ZnO exhibited an ellipsoidal shape.     

Carbon/PbO2 asymmetric electrochemical capacitor based on methanesulfonic acid electrolyte

A new hybrid electrochemical capacitor based on an activated carbon negative electrode, lead dioxide thin film and nanowire array positive electrode with an electrolyte made of a lead salt dissolved in methanesulfonic acid was investigated. It is shown that the maximum energy density and specific capacity of the C/PbO₂ nanowire system increase during the first 50 cycles before reaching their maximum values, which are 29 Wh kg⁻¹ and 34 F g⁻¹, respectively, at a current density of 10 mA cm⁻² and a depth of discharge (positive active electrode material) of 3.8%, that corresponds to a 22C rate. This is 7–8 times higher than the corresponding maximum values reached with a C/PbO₂ thin film cell operated in the same conditions. After an initial activation period, the performances of the C/PbO₂ nanowire system stay constant and do not show any sign of degradation during more than 5000 cycles. For comparison, the C/PbO₂ thin film system exhibits a 50% decrease of its performances in similar conditions.     

Failure mechanism of thin Al2O3 coatings grown by atomic layer deposition for corrosion protection of carbon steel

Combined analysis by electrochemical impedance spectroscopy (EIS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and field emission scanning electron microscopy (FESEM) of the corrosion protection provided to carbon steel by thin (50 nm) Al₂O₃ coatings grown by atomic layer deposition (ALD) and its failure mechanism is reported. In spite of excellent sealing properties, the results show an average dissolution rate of the alumina coating of ∼7 nm h⁻¹ in neutral 0.2 M NaCl and increasing porosity of the remaining layers with increasing immersion time. Alumina dissolution is triggered by the penetration of the solution via cracks/pinholes through the coating to the substrate surface where oxygen reduction takes place, raising the pH. At defective substrate surface sites of high aspect ratio and concentrated residual mechanical stress (along scratches) presumably exposing a higher steel surface fraction, localized dissolution of the coating is promoted by a more facile access of the solution to the substrate surface enhancing oxygen reduction. De-adhesion of the coating is also promoted in these sites by the ingress of the anodic dissolution trenching the steel surface. Localized corrosion of the alloy (i.e. pitting) is triggered prior to complete dissolution of the alumina film on the elsewhere still coated surface matrix.     

Mechanism of anodic oxidation of molybdenum in nearly-neutral electrolytes studied by electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy

Anodic oxidation of molybdenum in weakly acidic, nearly neutral and weakly alkaline electrolytes was studied by voltammetric and electrochemical impedance spectroscopic measurements in a wide potential and pH range. Current vs. potential curves were found to exhibit two pseudo-Tafel regions suggesting two parallel pathways of the dissolution process. Electrochemical impedance spectra indicated the presence of at least two reaction intermediates. X-ray photoelectron spectroscopic (XPS) results pointed to the formation of an oxide containing Mo(IV), Mo(V) and Mo(VI), the exact ratio between different valence states depending on potential and pH of the solution. A physico-chemical model of the processes is proposed and a set of kinetic equations for the steady-state current vs. potential curve and the impedance response are derived. The model is found to reproduce quantitatively the current vs. potential curves and impedance spectra at a range of potentials and pH and to agree qualitatively with the XPS results. Subject to further improvement, the model could serve as a starting point for the optimization of the electrochemical fabrication of functional molybdenum oxide coatings.     

Gas sensors based on thick films of semi-conducting single walled carbon nanotubes

A comparative study was made of sorted semi-conducting single walled carbon nanotube (SWCNT) films and unsorted SWCNT films for gas sensing applications. The transmission line method is used to monitor separately the SWCNTs film resistance and the contact resistance between electrodes and the SWCNTs, thus revealing that the sensing mechanism mainly relies on a modification of the tube conductivity during gas exposure. The fabricated sensors demonstrate a detection limit of 20 ppb NO₂ and 600 ppb NH₃ mainly attributed to experimental setup limitations. Moreover, semi-conducting nanotubes happened to be 2.5 times more sensitive to NH₃ than unsorted ones, thus proving that selectivity can be improved by sorting the SWCNTs. The temperature dependence of the sensor sensitivity was studied, and a good agreement was found between experimental results and the Langmuir adsorption model.