Synthesis and characterization of a new monometallic layered double hydroxide using manganese.

This article reports for the first time the synthesis of an LDH using only manganese as the divalent and trivalent metallic ion. Analysis of the pH, redox potential, and chemical composition during the oxidation of a manganese basic salt using persulfate indicates the oxidation of 1/3 of the initial MnII ions, in agreement with the paramagnetic structure and XPS analysis. Infrared, Raman spectra and thermogravimetric analysis results were similar to the ones obtained with Fe-LDH also known as green rust. X-Ray diffractograms and Rietveld refinement were used to determine the structure of this solid. Thermodynamic considerations predict that this solid could reduce nitrate into gaseous nitrogen without further reduction to ammonium or ammonia unlike what is observed for Fe-LDH.

As(V) and As(III) sequestration by starch functionalized magnetite nanoparticles: influence of the synthesis route onto the trapping efficiency.

We report the effect of the synthesis route of starch-functionalized magnetite nanoparticles (NPs) on their adsorption properties of As(V) and As(III) from aqueous solutions. NP synthesis was achieved by two different routes implying the alkaline precipitation of either a mixed Fe2+/Fe3+ salt solution (MC samples) or a Fe2+ salt solution in oxidative conditions (MOP samples). Syntheses were carried out with starch to Fe mass ratio (R) ranging from 0 to 10. The crystallites of starch-free MC NPs (14 nm) are smaller than the corresponding MOP (67 nm), which leads to higher As(V) sorption capacity of 0.3 mmol gFe -1 to compare with respect to 0.1 mmol gFe -1 for MOP at pH = 6. MC and MOP starch-functionalized NPs exhibit higher sorption capacities than a pristine one and the difference in sorption capacities between MOP and MC samples decreases with increasing R values. Functionalization tends to reduce the size of the magnetite crystallites and to prevent their agglomeration. Size reduction is more pronounced for MOP samples (67 nm (R0) to 12 nm (R10)) than for MC samples (14 nm (R0) to 9 nm (R10)). Therefore, due to close crystallite size, both MC and MOP samples, when prepared at R = 10, display similar As(V) (respectively, As(III)) sorption capacities close to 1.3 mmol gFe -1 (respectively, 1.0 mmol gFe -1). Additionally, according to the effect of pH on arsenic trapping, the electrostatic interactions appear as a major factor controlling As(V) adsorption while surface complexation may control As(III) adsorption.

Birnessite: A New Oxidant for Green Rust Formation.

Iron and manganese are ubiquitous in the natural environment. FeII-FeIII layered double hydroxide, commonly called green rust (GR), and MnIII-MnIV birnessite (Bir) are also well known to be reactive solid compounds. Therefore, studying the chemical interactions between Fe and Mn species could contribute to understanding the interactions between their respective biogeochemical cycles. Moreover, ferromanganese solid compounds are potentially interesting materials for water treatment. Here, a {Fe(OH)2, FeIIaq} mixture was oxidized by Bir in sulphated aqueous media in the presence or absence of dissolved O2. In oxic conditions for an initial FeII/OH- ratio of 0.6, a single GR phase was obtained in a first step; the oxidation kinetics being faster than without Bir. In a second step, GR was oxidised into various final products, mainly in a spinel structure. A partial substitution of Fe by Mn species was suspected in both GR and the spinel. In anoxic condition, GR was also observed but other by-products were concomitantly formed. All the oxidation products were characterized by XRD, XPS, and Mössbauer spectroscopy. Hence, oxidation of FeII species by Bir can be considered as a new chemical pathway for producing ferromanganese spinels. Furthermore, these results suggest that Bir may participate in the formation of GR minerals.

Solid-State NMR and DFT Combined for the Surface Study of Functionalized Silicon Nanoparticles.

Silicon nanoparticles (NPs) serve a wide range of optical, electronic, and biological applications. Chemical grafting of various molecules to Si NPs can help to passivate their reactive surfaces, "fine-tune" their properties, or even give them further interesting features. In this work, (1) H, (13) C, and (29) Si solid-state NMR spectroscopy has been combined with density functional theory calculations to study the surface chemistry of hydride-terminated and alkyl-functionalized Si NPs. This combination of techniques yields assignments for the observed chemical shifts, including the contributions resulting from different surface planes, and highlights the presence of physisorbed water. Resonances from near-surface (13) C nuclei were shown to be substantially broadened due to surface disorder and it is demonstrated that in an ambient environment hydride-terminated Si NPs undergo fast back-bond oxidation, whereas long-chain alkyl-functionalized Si NPs undergo slow oxidation. Furthermore, the combination of NMR spectroscopy and DFT calculations showed that the employed hydrosilylation reaction involves anti-Markovnikov addition of the 1-alkene to the surface of the Si NPs.

Unusual two-stage kinetics of ethylene adsorption on Si(100) unraveled by surface optical spectroscopy and Monte Carlo simulation.

The adsorption of ethylene on a Si(100)-2×1 surface in an ultrahigh vacuum has been monitored at room temperature by use of real-time surface differential reflectance spectroscopy, which clearly demonstrated that the adsorption follows a two-stage process. About half a monolayer is obtained for 1 L, while the second stage is much slower, yielding the complete monolayer for an exposure of ∼400 L. The kinetics over the full range has been successfully reproduced by a Monte Carlo calculation. The key point of this two-stage adsorption kinetic lies in the reduced adsorption probability (by a factor of several hundreds) on the Si dimers, neighbors of dimers which have already reacted, with respect to the adsorption probability on isolated dimers. This new kind of adsorption kinetics, due to a repulsion between already adsorbed molecules and additional molecules impinging on the surface, makes it a textbook case for a "cooperative" adsorption process.

Adsorption of phenylacetylene on Si(100)-2 x 1: kinetics and structure of the adlayer.

Direct adsorption of phenylacetylene on clean silicon surface Si(100)-2 x 1 is studied in ultrahigh vacuum (UHV). The combination of scanning tunnel microscopy (STM) and surface differential reflectance spectroscopy (SDRS) with Monte Carlo calculations are put together to draw a realistic kinetic model of the evolution of the surface coverage as a function of the molecular exposure. STM images of weakly covered surfaces provide evidence of two very distinct adsorption geometries for phenylacetylene, with slightly different initial sticking probabilities. One configuration is detected with STM as a bright spot that occupies two dangling bonds of a single dimer, whereas the other configuration occupies three dangling bonds of adjacent dimers. These data are used to implement a Monte Carlo model which further serves to design an accurate kinetic model. The resulting evolution toward saturation is compared to the optical data from surface differential reflectance spectroscopy (SDRS). SDRS is an in situ technique that monitors the exact proportion of affected adsorption sites and therefore gives access to the surface coverage which is evaluated at 0.65. We investigate the effect of surface temperature on this adsorption mechanism and show that it has no major effect either on kinetics or on structure, unless it passes the threshold of dissociation measured at ca. 200 degrees C. This offers a comprehensive image of the whole adsorption process of phenylacetylene from initial up to complete saturation.