Structural and Vibrational Properties of Carboxylates Intercalated into Layered Double Hydroxides: A Joint Computational and Experimental Study.

Layered double hydroxides (LDHs) are fascinating clay-like materials that display versatile properties, making them an extremely fertile playground for diverse applications, ranging from bio-compatible materials to the pharmaceutical industry to catalysis and photocatalysis. When intercalating organic and bio-organic species between the inorganic layers, such materials are named hybrid LDHs. The structure-property relation in these systems is particularly relevant, since most of the properties of the materials may be fine-tuned if a comprehensive understanding of the microscopic structure in the interlamellar space is achieved, especially with respect to the reorganization under water uptake (swelling). In this work, we combined experiments and simulations to rationalize the behavior of LDHs intercalating three carboxylates, the general structure of which can be given as [Mg4Al2(OH)12]A2-·XH2O (with A2- = succinate, aspartate, or glutamate and X representing increasing water content). Following this strategy, we were able to provide an interpretation of the different shapes observed for the experimental water adsorption isotherms and for the evolution of the infrared carboxylate band of the anions. Apart from small differences, due to the different reorganization of the conformational space under confinement, the behavior of the two amino acids is very similar. However, such behavior is quite different in the case of succinate. We were able to describe the different response of the anions, which has a significant impact on the isotherm and on the size of the interlamellar region, in terms of a different interaction mechanism with the inorganic layer.

Efficiency of saturated vertical-flow filters planted with Panicum maximum reeds for passive wastewater treatment.

A vertical-flow unit containing four filters filled with shale was used to study the removal of phosphorous, nitrogen and organic matter of an urban residual wastewater during a period of 90 days. The influence of both the shale granulometry and the plant density of Panicum Maximum were studied. The decrease of the shale granulometry led to a significant improvement of all the measured parameters, while the presence of plants did only influence the phosphate retention with a lower extent. By comparing the results to previous studies, we hypothesised that the effect of the root system of Panicum maximum would be different depending on the size and the depth of the reactors. For practical application, adjusting the material granulometry was proposed to be the most important parameter for improving the filtration efficiency. Concomitantly, adjusting the plant density helps to control the clogging percentage of the filters.

Enhanced catalytic oxidation ability of ternary layered double hydroxides for organic pollutants degradation.

Co(2+) and Cu(2+) substituted MgAl layered double hydroxides with an M(2+)/M(3+) atomic ratio of 2.0 were synthesized by a co-precipitation method and fully characterized using various techniques including powder X-ray diffraction, ICP-AES analysis, FT-IR, DR UV-Vis spectroscopy, N2 adsorption-desorption and transmission electron microscopy. The materials revealed a good crystallinity with no phase impurity and successful substitution of cobalt and copper ions in the framework of binary LDH with the target ratio of metals in the sheet. The adsorption characteristics (kinetic and isotherm) and the catalytic oxidation of organic pollutants, methylene blue (cationic dye) and orange II (anionic) were carried out to investigate a potential use of LDH materials as catalysts. In particular, Co3Cu1Al2 LDH exhibited an excellent catalytic activity towards catalytic dye degradation, especially for orange II with good stability and reusability over several times. Furthermore, this LDH material showed good catalytic performance for several chlorophenol compounds, suggesting its practical application in wastewater treatment. Therefore, layered double hydroxides substituted with Co(2+) and Cu(2+) could be promising candidates in various applications, such as the abatement of organic pollutants.

The Raman spectrum of CaCO3 polymorphs calcite and aragonite: a combined experimental and computational study.

Powder and single crystal Raman spectra of the two most common phases of calcium carbonate are calculated with ab initio techniques (using a "hybrid" functional and a Gaussian-type basis set) and measured both at 80 K and room temperature. Frequencies of the Raman modes are in very good agreement between calculations and experiments: the mean absolute deviation at 80 K is 4 and 8 cm(-1) for calcite and aragonite, respectively. As regards intensities, the agreement is in general good, although the computed values overestimate the measured ones in many cases. The combined analysis permits to identify almost all the fundamental experimental Raman peaks of the two compounds, with the exception of either modes with zero computed intensity or modes overlapping with more intense peaks. Additional peaks have been identified in both calcite and aragonite, which have been assigned to (18)O satellite modes or overtones. The agreement between the computed and measured spectra is quite satisfactory; in particular, simulation permits to clearly distinguish between calcite and aragonite in the case of powder spectra, and among different polarization directions of each compound in the case of single crystal spectra.

pH influence on the complexation site of Al(III) with protocatechuic acid. A spectroscopic and theoretical approach.

Electronic spectroscopy techniques with the aid of quantum chemical calculations, and notably the Time-Dependent Density Functional Theory, can be used to probe the structure of metal complexes in solution. Here, we report the characterization of Al(III)-protocatechuate in aqueous solution, at pH=6.5. The exploitation of the UV-vis spectra of the system by chemometric methods highlights the formation of a single complex of stoichiometry 1:1. From different structural hypothesis, the comparison of theoretical and experimental spectra shows that Al(III) forms a monodentate complex with the carboxylate function. This hypothesis is confirmed by the calculation of the complexation reaction pathways. Previous studies report the formation of a chelate involving the ortho-dihydroxyl group, at pH=3.5. These results illustrate the important dependence of the protonation state of the carboxylic function on the Al(III) fixation site on the studied ligand.

Versatile stereoselective cycloadditions between heterocumulenes and phosphagermaallene Tip(tBu)Ge=C=PMes*: experimental and theoretical investigations.

Phosphagermaallene Tip(tBu)Ge=C=PMes* 1 (Tip=2,4,6-triisopropylphenyl, Mes*=2,4,6-tri-tert-butylphenyl) reacts with phenyl isocyanate and tert-butyl isocyanate by a [2+2] cycloaddition that involves the Ge=C and C=O double bonds to afford 1-oxa-2-germacyclobutanes 2 and 3. With N,N'-dicyclohexylcarbodiimide, a [2+2] cycloaddition is observed between the Ge=C and C=N unsaturations to lead to 1-aza-2-germacyclobutane 6 with exocyclic P=C and C=N double bonds. In sharp contrast, 1 reacts with phenyl isothiocyanate, ethyl isothiocyanate, and carbon disulfide according to a [3+2] cycloaddition that involves the whole Ge=C=P unit and the C=S double bond to give transient phosphagermacarbenes (PGeHCs) 11, 12, and 13. These new PGeHCs undergo C-H insertions into one o-tBu group of Mes* (in the case of 11 and 12) or one o-iPr group of Tip (in the case of 13) with formation of tricyclic compounds 8, 9, and 10, respectively. The reaction mechanisms that involve 1 and the phenyl isocyanate and the phenyl isothiocyanate are described and their regioselectivity is explained by theoretical calculations.

Toward a better understanding of the regioselectivity of the Al(III)-protocatechuic acid complexation reaction.

Protocatechuic acid presents two complexing sites in competition to fix metal: the carboxylic and catechol functions. Even in acidic aqueous medium, where the free ligand is fully protonated, Al(III) forms a chelate with the doubly deprotonated catechol group. To gain a better understanding of the complexation mechanism and to explain the regioselectivity of the reaction, reaction pathways involving either the catechol group or the carboxylic one have been calculated at the B3LYP/6-31G(d,p) level of theory. All the intermediate species have been identified, and both processes present the following different steps: metal attack with the coordination of Al(III) to an oxygen atom; deprotonation of hydroxyl groups; ring closure to form a chelate. Whatever the complexing site, a bidentate complex is more stable than a monodentate one. From an energetic point of view, the reaction pathway corresponding to a chelate formation with the catechol function is favored; notably the energy barrier necessary to close the ring involving the metal ion is calculated to be lower than that of carboxyl function.