Unveiling redox mechanism at the iron centers in the mechanochemically activated conversion of CO2 in the presence of olivine.

The transformation of olivine during the conversion of CO2 to light hydrocarbons activated by mechanochemical treatments at different impact frequencies was studied by a combination of several complementary characterization methods including X-ray diffraction, Raman and 57Fe Mössbauer spectroscopy. Several olivine samples were studied as a function of the milling time, indicating the gradual transformation of FeII-containing olivine into new FeIII-containing weathering products including iron oxides, magnesium iron carbonates and silicates. The results presented here complement those of a previous study on the weathering process of olivine promoted by mechanochemical activation, by demonstrating the role of the redox activity of the iron species during the activation process. These additional spectroscopic results allow us to thoroughly understand the complex weathering mechanism and to correlate it with the efficiency of the CO2 conversion and storage properties of mechanochemically activated olivine. Supplementary Information: The online version contains supplementary material available at 10.1007/s10853-022-06962-x.

In situ synchrotron radiation investigation of V2O5-Nb2O5 metastable compounds: transformational kinetics at high temperatures with a new structural solution for the orthorhombic V4Nb20O60 phase.

Due to the considerable interest in vanadium niobium oxides as a lithium storage material, the kinetics and transformation processes of the V2O5-5Nb2O5 system have been investigated by in situ synchrotron powder X-ray diffraction. The diffraction data after the thermal treatments selected with a view on the most significant features were supplemented with specific ex situ experiments conducted using a laboratory rotating anode X-ray diffractometer. The morphological changes of the mixed powders assuming an amorphous and nanocrystalline solid solution structure as a function of the temperature were inspected by scanning electron microscopy observations. The structural solution of the powder diffraction pattern of the phase recorded in situ at a temperature of about 700 °C was compatible with an orthorhombic crystal structure with the space group Amm2. The obtained lattice parameters for this structure were a = 3.965 Å; b = 17.395 Å, c = 17.742 Å, and the cell composition was V4Nb20O60, Pearson symbol oA84, and density = 4.10 g cm-3. In this structure, while the niobium atoms may be four-, five-, and six-fold coordinated by oxygen atoms, the vanadium atoms were six-fold or seven-fold coordinated. At the temperature of 800 °C and just above, the selected 1 : 2 and 1 : 3 V2O5-Nb2O5 compositions, respectively, returned mostly a tetragonal VNb9O25 phase, in line with earlier observations conducted for determination of the stability phase diagram of such quasi-binary systems.

Magnesium imide: synthesis and structure determination of an unconventional alkaline earth imide from decomposition of magnesium amide.

Magnesium imide (MgNH) was produced by monitoring the decomposition process of magnesium amide with in situ neutron diffraction. Significant changes in the structure of magnesium amide are detected during heat treatment and eventually result in the formation of crystalline MgNH. A model for the crystal structure of magnesium imide (MgNH) is presented for the first time. Remarkably, magnesium imide offers unique structural features similar to the cyclosilicate class and can be described as a porous solid formed by a sequence of linked chains of face sharing Mg(6)N(6) hexagonal prism clusters.

Cremation practices coexisting at the S'Illot des Porros Necropolis during the Second Iron Age in the Balearic Islands (Spain).

The necropolis of S'Illot des Porros, one of the most important prehistoric funerary sites of the Balearic Islands (Spain), was in use from the VIth and Vth century BCE until the Ist century CE. Located in a funerary area which contains two cementeries and one sanctuary, this site is constituted by three funerary chambers named A, B and C, respectively. Investigations on all the human burnt bone remains of the chambers, carried out mainly by the X-ray diffraction and supplemented in some cases by Fourier Transform Infrared spectroscopy pointed to the simultaneous use of inhumation and cremation funerary rites, probably due to existing social differences. In particular, it was argued that the chambers were differentiated, i.e., B was dedicated to inhumations and A to cremations, the cremations found in chamber B very likely being a result of a cleaning-purification of the burial area. Moreover, chamber C, which is the most ancient (IVth century BCE) and with the largest number of inhumed remains, contains the smallest number of remains that were exposed to fire and just in one case it seems possible to attribute a genuine high-temperature cremation.

Study of sorption processes and FT-IR analysis of arsenate sorbed onto red muds (a bauxite ore processing waste).

In this study we evaluated the arsenate adsorption capacity of red muds (RM), wastes tailing from the alumina production, at different pH values (4, 7, and 10). RM samples were artificially enriched in batch tests with solutions containing increasing concentrations of As(V). The pH of the solution significantly affected the adsorption, which increased with the decrease of pH. Moreover a sequential extraction procedure [H(2)O; (NH(4))(2)SO(4); NH(4)H(2)PO(4); NH(4)(+)-oxalate; NH(4)(+)-oxalate+ascorbic acid] was applied to RM samples exchanged with arsenate. Using this approach it was shown that low concentrations of arsenate sorbed in RM were present as water soluble and exchangeable fractions, while NH(4)(+)-oxalate and NH(4)(+)-oxalate+ascorbic acid extracted most of the adsorbed arsenate from RM at different pH values. Besides, FT-IR spectroscopy was used to better understand the nature of RM surface configuration after As(V) sorption. In the FT-IR spectra the presence of As(V) species was highlighted by a well resolved band at 865 cm(-1). The intensity and broadness of this band increased at the decreasing of pH. This band could be related to nu(As-O) vibration of an inner-sphere Al-O-As complex and/or due to As-O bonds of the adsorbed As(V) species on Fe oxides of RM samples.