Probing the Structural Order of Half-Heusler Phases in Sb-Doped (Ti,Zr,Hf)NiSn Thermoelectrics

The nanostructural features of a mechanically alloyed Sb-doped (Ti0.4Zr0.6)0.7Hf0.3NiSn thermoelectric (TE) Half-Heusler (HH) compound were addressed using Transmission Electron Microscopy (TEM) coupled with Energy Dispersive Spectroscopy measurements and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. The EXAFS measurements at the Ni-K, Sn-K, Zr-K, and Hf-L3-edge were implemented in an effort to reveal the influence of Hf and Zr incorporation into the crystal with respect to their previously measured TE properties. The substitution of Ti by Hf and Zr is expected to yield local lattice distortions due to the different atomic sizes of the dopants or/and electronic charge redistribution amongst the cations. However, the material is characterised by a high degree of crystallinity in both the short and long-range order, on average, and the nominal stoichiometry is identified as (Zr0.42Hf0.30Ti0.28)NiSn0.98Sb0.02. The synergistic effect of minimization of extended structural defects or lattice distortions and considerable alloying-induced point defect population contributes to the improved TE properties and leads to the previously reported enhancement of the figure of merit of the mixed HHs

On the Nanostructure of Cu in Ti<sub>x</sub>Cu<sub>1-x</sub> and TiN/Cu Films: A XAFS Study

The effect of chemical composition on the bonding environment of Cu, in a series of Ti1-x Cux and TiN/Cu films, is studied using X-Ray Absorption Spectroscopies (XAFS) at the Cu-K-edge. The EXAFS analysis reveals that in all studied samples Cu is amorphous. However, its bonding environment depends on the chemical composition. More specifically, in the Ti1-xCux films, Cu is coordinated with Ti and Cu and belongs both to intermetallic TiCu and to an amorphous Cu matrix. The coordination number of Cu, i.e., the sum of Ti and Cu first neighbours, increases systematically from 6.3 ± 0.7 to 10.6 ± 0.9 when the Cu content increases from 24.1 to 52.7 at%. On the contrary, in the TiN/Cu films, the type of atoms that consists the 1st nearest neighbour shell of Cu varies as a function of the Cu concentration. More specifically, in the TiN/Cu film with the lowest Cu content (27.3 at%), intermetallic TiCu is detected. At intermediate Cu concentration (37.8 at%), Cu is bonded to both Ti and Cu atoms. Finally, in the TiN/Cu film with the highest Cu content (67.7 at%), Cu is metallic. </jats:p

Continuous flow process of Cr(VI) removal from drinking water through reduction onto FeOOH by inorganic sulfur reductants

Abstract In this study, the implementation of an iron oxy-hydroxide (FeOOH) as a surface catalyst for Cr(VI) reduction by inorganic sulfur reductants (ISRs) was investigated. Batch Cr(VI) removal tests, performed to evaluate and compare the efficiency of ISRs in the presence of FeOOH, qualified Na2S2O4 as the optimum for drinking water treatment. Application of Na2S2O4 in continuous flow rapid small scale column tests, using a FeOOH adsorbent at pH 7 ± 0.1 and artificial (resembling natural) water matrix, verified the high potential for Cr(VI) removal at sub-ppb level. Indeed, a 15 mg S/L Na2S2O4 dose diminished an initial Cr(VI) concentration of 100 μg/L below the method's detection limit of 1.4 μg/L at least for 105 bed volumes. X-ray absorption fine structure spectroscopy revealed that Cr(VI) forms outer sphere complexes, while Cr(III) is involved in 2E, 2C and 1 V geometries with the surface Fe-oxyhydroxyl groups. It can, therefore, be concluded that FeOOH attracts Cr(VI) to its surface via physisorption, offering a solid surface that promotes the transfer of electrons through bridging ions. Thus, when Na2S2O4 is added in the system, Cr(VI) is reduced to Cr(III), which is subsequently chemisorbed onto the FeOOH surface.</jats:p

Chromium (VI) removal from aqueous solutions using a polyethylenimine - epichlorohydrin resin

The ability of a synthesized polyethylenimine - epichlorohydrin resin to remove Cr(VI) from aqueous solutions was investigated in absence (initial pH 2 to 7) and presence of background electrolytes (NaNO3 and Na2SO4 solutions of initial pH 3 and 6). The determined Cr-uptake was significantly higher than the one reported for the majority of other sorbents. The photo-metrically determined uptake data were modeled by the Langmuir, Redlich-Peterson, Langmuir-Freundlich, and Toth equations. The modeling results did not point out any preference to one specific model in terms of the goodness-of-fit and the prediction of maximum sorption capacity. The Cr-sorption kinetics was investigated at 15, 25, 35 and 45 oC using 51Cr-labeled solutions and γ-ray spectroscopy. The Cr-sorption was very fast at all studied temperatures and well reproduced by the pseudo-second order kinetics equation. Rate constant and activation energy values were calculated using the experimental data. The Cr-loaded resin was also examined by XRD, XPS, XAFS and SEM/EDS. The XPS and XAFS investigations indicated a partial reduction of Cr(VI) to Cr(III). The environmental compatibility of the Cr-loaded resin was examined using the EPA-TCLP method. The Cr-binding by the resin was very stable and regeneration attempts by HCl solutions of pH 3 were rather unsuccessful

Se(IV)/Se(VI) adsorption mechanisms on natural and on Ca-modified zeolite for Mediterranean soils amended with the modified zeolite: prospects for agronomic applications

Abstract In the present study, the ability of a modified CaCl2 zeolite (Ca-Z) to both increase Se(IV) availability and restrict Se(VI) mobility in soils is examined. As it was resulted from batch experiments and verified by X-ray absorption fine structure (XAFS) and X-ray fluorescence (XRF) spectroscopies, higher amounts of both Se species adsorbed on Ca-Z compared to natural zeolite (Z-N) forming outer-sphere complexes while the oxidation state did not alter during agitation of samples. Thereafter, Ca-Z was incorporated in six Greek soils, divided into acid and alkaline, at a 20% (w/w) rate and a series of equilibrium batch experiments were performed with soils alone and soils-Ca-Z mixtures to investigate sorption and desorption processes and mechanisms. The acid soils, either treated with Ca-Z or not, adsorbed higher amounts of Se(IV) than alkaline ones, whereas soils alone did not adsorb Se(VI) but impressively high adsorption of Se(VI) occurred in the Ca-Z-treated soils. Desorption of Se(IV) was higher from the Ca-Z-treated soils and especially from the acid soils. Higher distribution coefficients of desorption than the distribution coefficients of sorption were observed, clearly pointing to a hysteresis mechanism. The experimental data fitted with Langmuir and Freundlich isotherms. In the presence of Ca-Z, the Langmuir qm values increased indicating higher Se(IV) retention while Langmuir bL values decreased suggesting lower bonding strength and higher Se(IV) mobility. Overall, treating the soils with Ca-Z increased Se(IV) adsorption and mobility whereas it provided sites for Se(VI) adsorption that did not exist in the studied soils.</jats:p