Cédric Malherbe

A facile and fast electrochemical route to produce functional few-layer graphene sheets for lithium battery anode application

A simple approach for the production of polymer functionalized graphene nanosheets is reported. The resulting polyacrylonitrile chemisorbed on graphene sheets is made of 1 to 2 layers, with a large majority of graphene single-layers. This novel functionalized graphene exhibits good cycling stability as an anode in Li-ion batteries without a conductive additive or binder.

Online Monitoring of Heterogeneous Polymerizations in Supercritical Carbon Dioxide by Raman Spectroscopy

A novel setup is described to monitor the kinetics of homogeneous and heterogeneous reactions online using Raman spectroscopy under high pressure. The arrangement is based on a high-pressure reactor equipped with a sapphire window in combination with a mobile probe that allows the collection of the back-scattered Raman signal at 360°.

Biogeological Analysis of Desert Varnish Using Portable Raman Spectrometers

Desert varnishes are thin, dark mineral coatings found on some rocks in arid or semi-arid environments on Earth. Microorganisms may play an active role in their formation, which takes many hundreds of years. Their mineral matrix may facilitate the preservation of organic matter and is therefore of great relevance to martian exploration. Miniaturized Raman spectrometers (which allow nondestructive analysis of the molecular composition of a specimen) will equip rovers in forthcoming planetary exploration missions. In that context, and for the first time, portable Raman spectrometers operating in the green visible (532 nm as currently baselined for flight) and in the near-infrared (785 nm) were used in this study to investigate the composition (and substrate) of several samples of desert varnish. Rock samples that were suspected (and later confirmed) to be coated with desert varnish were recovered from two sites in the Mojave Desert, USA. The portable spectrometers were operated in flight-representative acquisition modes to identify the key molecular components of the varnish. The results demonstrate that the coatings typically comprise silicate minerals such as quartz, plagioclase feldspars, clays, ferric oxides, and hydroxides and that successful characterization of the samples can be achieved by using flightlike portable spectrometers for both the 532 and 785 nm excitation sources. In the context of searching for spectral signatures and identifying molecules that indicate the presence of extant and/or extinct life, we also report the detection of β-carotene in some of the samples. Analysis complications caused by the presence of rare earth element photoluminescence (which overlaps with and overwhelms the organic Raman signal when a 785 nm laser is employed) are also discussed.

Determination of the Al2O3 Content in NaF–AlF3–CaF2–Al2O3 Melts at 950 °C by Raman Spectroscopy

The in situ control of the chemical composition of industrial aluminum smelter is a challenge mainly for physicochemical reasons: high temperature, high surrounding electromagnetic field, and the highly corrosive molten salt electrolyte to deal with. In previous works, we proposed that Raman spectroscopy is a method of choice that could be adapted to real smelters. The laboratory study presented here relies on reproducible Raman spectra recorded on molten mixtures whose compositions are identical to those used during the production of aluminum. A normalization procedure for the Raman spectra is proposed based on the equilibria taking place in the bath. In addition, we discuss two quantitative models to determine the alumina content from the Raman spectra of the molten NaF-AlF3-CaF2-Al2O3 electrolytes. Univariate and multivariate approaches are applied to determine both the COx (alumina content) and the CR (NaF/AlF3 molar ratio) by Raman spectroscopy without referring to an additional internal reference of intensity. The procedure was successfully tested and validated on industrial samples.

Direct determination of the NaF/AlF3 molar ratio by raman spectroscopy in NaF-AlF3-CaF2 melts at 1000° C

For the last 40 years, Raman spectroscopy has been very useful in investigating the structure of corrosive molten salts, such as the cryolite-based melts widely used as electrolyte in the Hall-Heroult process. Even if this process remains the most economically efficient for metallic aluminum electro-production, it suffers from a high energy loss, which is dependent on the melt composition. Therefore, controlling the chemical composition of the electrolyte is essential. The present paper proposes to apply Raman spectroscopy for the direct determination of the NaF-AlF3 molar ratio in NaF-AlF3-CaF2-based melts. Despite the experimental difficulties, a calibration curve based on equilibria taking place in the melt has been developed and the procedure has been successfully compared to industrial samples of known compositions. The possible exportation of the laboratory scale procedure to an industrial environment application for the control of the Hall-Heroult process is finally discussed.

Tentative Determination of the Acidity Level in Room Temperature Ionic Liquids by Electrochemical Methods

In our attempt to evaluate the acidity levels reached by acidified ionic liquids (BMImBF4, BMImNTf2 and BMImOTf + HOTf or HNTf2), the uncertainty on the pKas of the indicators needed for the Hammett spectrophotometric procedure was pointed out. As consequence another method is proposed, based on the H + /H2 couple potential measurement. In this purpose, if dynamic methods failed mainly for lack of sufficient reversibility, potentiometry with a hydrogen electrode gave meaningful results. The R0(H + ) Strehlow function, could be calculated, using the Fc + -Fc couple as reference assumed as solvent independent. The obtained results show that i) the acidities are much higher than those in water; ii) the acidities measured by the hydrogen electrode are higher than those measured by the Hammett method; iii) the sequence of acidities for solutions of similar content of added acid is still BF4 > NTf2 - > OTf - as previously measured with the Hammett method.