13 research outputs found
Adsorption of Selenium and Strontium on Goethite: EXAFS Study and Surface Complexation Modeling of the Ternary Systems
Knowledge of the geochemical behavior of selenium and strontium is critical for the safe disposal of radioactive wastes. Goethite, as one of the most thermodynamically stable and commonly occurring natural iron oxy-hydroxides, promisingly retains these elements. This work comprehensively studies the adsorption of Se(IV) and Sr(II) on goethite. Starting from electrokinetic measurements, the binary and ternary adsorption systems are investigated and systematically compared via batch experiments, EXAFS analysis, and CD-MUSIC modeling. Se(IV) forms bidentate inner-sphere surface complexes, while Sr(II) is assumed to form outer-sphere complexes at low and intermediate pH and inner-sphere complexes at high pH. Instead of a direct interaction between Se(IV) and Sr(II), our results indicate an electrostatically driven mutual enhancement of adsorption. Adsorption of Sr(II) is promoted by an average factor of 5 within the typical groundwater pH range from 6 to 8 for the concentration range studied here. However, the interaction between Se(IV) and Sr(II) at the surface is two-sided, Se(IV) promotes Sr(II) outer-sphere adsorption, but competes for inner-sphere adsorption sites at high pH. The complexity of surfaces is highlighted by the inability of adsorption models to predict isoelectric points without additional constraints
Optimizing Ni-Fe-Ga alloys into NiFeGa for the hydrogenation of CO into methanol
A screening study of the catalytic performance of ternary alloy nanoparticles containing nickel, iron and gallium supported on silica for methanol synthesis from CO and H was performed. Catalysts were prepared by incipient wetness impregnation and subsequently reduced in H before catalytic testing. NiFeGa showed the best performance of the tested catalysts in terms of methanol yield. An optimization of the preparation was done to improve activity and selectivity, reaching a performance close to that of commercially available Cu/ZnO/AlO/MgO at low reaction temperatures and pressure. Extensive in situ characterisation using environmental TEM, in situ XRD and in situ EXAFS of the formation of the NiFeGa catalyst explains an optimal reduction temperature of 550 °C: warm enough that the three atomic species will form an alloy while cold enough to prevent the catalyst from sintering during the formation
The mechanism of Fe induced bond stability of uranyl( v )
The stabilization of uranyl(V) (UO21+) by Fe(II) in natural systems remains an open question in uranium chemistry. Stabilization of UVO21+ by Fe(II) against disproportionation was also demonstrated in molecular complexes. However, the relation between the Fe(II) induced stability and the change of the bonding properties have not been elucidated up to date. We demonstrate that U(V) – oaxial bond covalency decreases upon binding to Fe(II) inducing redirection of electron density from the U(V) – oaxial bond towards the U(V) – equatorial bonds thereby increasing bond covalency. Our results indicate that such increased covalent interaction of U(V) with the equatorial ligands resulting from iron binding lead to higher stability of uranyl(V). For the first time a combination of U M4,5 high energy resolution X-ray absorption near edge structure (HR-XANES) and valence band resonant inelastic X-ray scattering (VB-RIXS) and ab initio multireference CASSCF and DFT based computations were applied to establish the electronic structure of iron-bound uranyl(V)
MRI of Arterial Flow Reserve in Patients with Intermittent Claudication: Feasibility and Initial Experience
Objectives: The aim of this work was to develop a MRI method to determine arterial flow reserve in patients with intermittent claudication and to investigate whether this method can discriminate between patients and healthy control subjects. Methods: Ten consecutive patients with intermittent claudication and 10 healthy control subjects were included. All subjects underwent vector cardiography triggered quantitative 2D cine MR phase-contrast imaging to obtain flow waveforms of the popliteal artery at rest and during reactive hyperemia. Resting flow, maximum hyperemic flow and absolute flow reserve were determined and compared between the two groups by two independent MRI readers. Also, interreader reproducibility of flow measures was reported. Results: Resting flow was lower in patients compared to controls (4.961.6 and 11.163.2 mL/s in patients and controls, respectively (p,0.01)). Maximum hyperemic flow was 7.362.9 and 16.463.2 mL/s (p,0.01) and the absolute flow reserve was 2.461.6 and 5.361.3 mL/s (p,0.01), respectively in patients and controls. The interreader coefficient of variation was below 10 % for all measures in both patients and controls. Conclusions: Quantitative 2D MR cine phase-contrast imaging is a promising method to determine flow reserve measures in patients with peripheral arterial disease and can be helpful to discriminate patients with intermittent claudication fro
Adsorption of Selenium and Strontium on Goethite: EXAFS Study and Surface Complexation Modeling of the Ternary Systems
Knowledge
of the geochemical behavior of selenium and strontium
is critical for the safe disposal of radioactive wastes. Goethite,
as one of the most thermodynamically stable and commonly occurring
natural iron oxy-hydroxides, promisingly retains these elements. This
work comprehensively studies the adsorption of SeÂ(IV) and SrÂ(II) on
goethite. Starting from electrokinetic measurements, the binary and
ternary adsorption systems are investigated and systematically compared
via batch experiments, EXAFS analysis, and CD-MUSIC modeling. SeÂ(IV)
forms bidentate inner-sphere surface complexes, while SrÂ(II) is assumed
to form outer-sphere complexes at low and intermediate pH and inner-sphere
complexes at high pH. Instead of a direct interaction between SeÂ(IV)
and SrÂ(II), our results indicate an electrostatically driven mutual
enhancement of adsorption. Adsorption of SrÂ(II) is promoted by an
average factor of 5 within the typical groundwater pH range from 6
to 8 for the concentration range studied here. However, the interaction
between SeÂ(IV) and SrÂ(II) at the surface is two-sided, SeÂ(IV) promotes
SrÂ(II) outer-sphere adsorption, but competes for inner-sphere adsorption
sites at high pH. The complexity of surfaces is highlighted by the
inability of adsorption models to predict isoelectric points without
additional constraints