A comparative study of experimental configurations in synchrotron pair distribution function

The identification and quantification of amorphous components and nanocrystalline phases with very small crystal sizes, smaller than ~3 nm, within samples containing crystalline phases is very challenging. However, this is important as there are several types of systems that contain these matrices: building materials, glass-ceramics, some alloys, etc. The total scattering synchrotron pair distribution function (PDF) can be used to characterize the local atomic order of the nanocrystalline components and to carry out quantitative analyses in complex mixtures. Although the resolution in momentum transfer space has been widely discussed, the resolution in the interatomic distance space has not been discussed to the best of our knowledge. Here, we report synchrotron PDF data collected at three beamlines in different experimental configurations and X-ray detectors. We not only discuss the effect of the resolution in Q-space, Qmax ins of the recorded data and Qmax of the processed data, but we also discuss the resolution in the interatomic distance (real) space. A thorough study of single-phase crystalline nickel used as standard was carried out. Then, selected cement-related samples including anhydrous tricalcium and dicalcium silicates, and pastes derived from the hydration of tricalcium silicate and ye’elimite with bassanite were analyzed.This work is part of the PhD of Mr. Jesus D. Zea-Garcia. This work was supported by Spanish MINECO and FEDER [BIA2017-82391-R research project and I3 [IEDI-2016-0079] program]

A Bow Shock Nebula Around a Compact X-Ray Source in the Supernova Remnant IC443

We present spectra and high resolution images of the hard X-ray feature along the southern edge of the supernova remnant IC443. Data from the Chandra X-ray Observatory reveal a comet-shaped nebula of hard emission, which contains a softer point source at its apex. We also present 20cm, 6cm, and 3.5cm images from the Very Large Array that clearly show the cometary nebula. Based on the radio and X-ray morphology and spectrum, and the radio polarization properties, we argue that this object is a synchrotron nebula powered by the compact source that is physically associated with IC443. The spectrum of the soft point source is adequately but not uniquely fit by a black body model (kT=0.71 +/- 0.08 keV, L=(6.5 +/- 0.9) * 10^31 erg/s). The cometary morphology of the nebula is the result of the supersonic motion of the neutron star (V_NS=250 +/- 50 km/s), which causes the relativistic wind of the pulsar to terminate in a bow shock and trail behind as a synchrotron tail. This velocity is consistent with an age of 30,000 years for the SNR and its associated neutron star.Comment: 9 pages, 5 figures, accepted for publication in the ApJ Letter

Versatile Coordination of Cyclopentadienyl-Arene Ligands and Its Role in Titanium-Catalyzed Ethylene Trimerization

Cationic titanium(IV) complexes with ansa-(η5-cyclopentadienyl,η6-arene) ligands were synthesized and characterized by X-ray crystallography. The strength of the metal-arene interaction in these systems was studied by variable-temperature NMR spectroscopy. Complexes with a C1 bridge between the cyclopentadienyl and arene moieties feature hemilabile coordination behavior of the ligand and consequently are active ethylene trimerization catalysts. Reaction of the titanium(IV) dimethyl cations with CO results in conversion to the analogous cationic titanium(II) dicarbonyl species. Metal-to-ligand backdonation in these formally low-valent complexes gives rise to a strongly bonded, partially reduced arene moiety. In contrast to the η6-arene coordination mode observed for titanium, the more electron-rich vanadium(V) cations [cyclopentadienyl-arene]V(NiPr2)(NC6H4-4-Me)+ feature η1-arene binding, as determined by a crystallographic study. The three different metal-arene coordination modes that we experimentally observed model intermediates in the cycle for titanium-catalyzed ethylene trimerization. The nature of the metal-arene interaction in these systems was studied by DFT calculations.

Alkaline-earth phosphonate MOFs with reversible hydration-dependent fluorescence

A new rigid tritopic phosphonic ligand, 2,4,6-tris(4-phosphonophenyl)pyridine (H6L), was synthesized and used to assemble isostructural barium (1) and strontium (2) phosphonate metal organic frameworks that exhibit fully reversible and selective water-dependent fluorescence red-shift at room temperature

Behavior and Impact of Zirconium in the Soil–Plant System: Plant Uptake and Phytotoxicity

Because of the large number of sites they pollute, toxic metals that contaminate terrestrial ecosystems are increasingly of environmental and sanitary concern (Uzu et al. 2010, 2011; Shahid et al. 2011a, b, 2012a). Among such metals is zirconium (Zr), which has the atomic number 40 and is a transition metal that resembles titanium in physical and chemical properties (Zaccone et al. 2008). Zr is widely used in many chemical industry processes and in nuclear reactors (Sandoval et al. 2011; Kamal et al. 2011), owing to its useful properties like hardness, corrosion-resistance and permeable to neutrons (Mushtaq 2012). Hence, the recent increased use of Zr by industry, and the occurrence of the Chernobyl and Fukashima catastrophe have enhanced environmental levels in soil and waters (Yirchenko and Agapkina 1993; Mosulishvili et al. 1994 ; Kruglov et al. 1996)

Cation-swapped homogeneous nanoparticles in perovskite oxides for high power density

Exsolution has been intensively studied in the fields of energy conversion and storage as a method for the preparation of catalytically active and durable metal nanoparticles. Under typical conditions, however, only a limited number of nanoparticles can be exsolved from the host oxides. Herein, we report the preparation of catalytic nanoparticles by selective exsolution through topotactic ion exchange, where deposited Fe guest cations can be exchanged with Co host cations in PrBaMn1.7Co0.3O5+delta. Interestingly, this phenomenon spontaneously yields the host PrBaMn1.7Fe0.3O5+delta, liberating all the Co cations from the host owing to the favorable incorporation energy of Fe into the lattice of the parent host (Delta E-incorporation = -0.41 eV) and the cation exchange energy (Delta E-exchange = -0.34 eV). Remarkably, the increase in the number of exsolved nanoparticles leads to their improved catalytic activity as a solid oxide fuel cell electrode and in the dry reforming of methane

Experimental Findings On Minor Actinide And Lanthanide Separations Using Ion Exchange

This project seeks to determine if inorganic or hybrid inorganic ion-exchange materials can be exploited to provide effective americium and curium separations. Specifically, we seek to understand the fundamental structural and chemical factors responsible for the selectivity of the tested ion-exchange materials for actinide and lanthanide ions. During FY13, experimental work focused in the following areas: (1) investigating methods to oxidize americium in dilute nitric acid with subsequent ion-exchange performance measurements of ion exchangers with the oxidized americium and (2) synthesis, characterization and testing of ion-exchange materials. Ion-exchange materials tested included alkali titanates, alkali titanosilicates, carbon nanotubes and group(IV) metal phosphonates. Americium oxidation testing sought to determine the influence that other redox active components may have on the oxidation of Am(III). Experimental findings indicated that Pu(IV) is oxidized to Pu(VI) by peroxydisulfate, but there are no indications that the presence of plutonium affects the rate or extent of americium oxidation at the concentrations of peroxydisulfate being used. Tests also explored the influence of nitrite on the oxidation of Am(III). Given the formation of Am(V) and Am(VI) in the presence of nitrite, it appears that nitrite is not a strong deterrent to the oxidation of Am(III), but may be limiting Am(VI) by quickly reducing Am(VI) to Am(V). Interestingly, additional absorbance peaks were observed in the UV-Vis spectra at 524 and 544 nm in both nitric acid and perchloric acid solutions when the peroxydisulfate was added as a solution. These peaks have not been previously observed and do not correspond to the expected peak locations for oxidized americium in solution. Additional studies are in progress to identify these unknown peaks. Three titanosilicate ion exchangers were synthesized using a microwave-accelerated reaction system (MARS�) and determined to have high affinities for lanthanide ions in dilute nitric acid. The K-TSP ion exchanger exhibited the highest affinity for lanthanides in dilute nitric acid solutions. The Ge-TSP ion exchanger shows promise as a material with high affinity, but additional tests are needed to confirm the preliminary results. On the other hand, carbon nanotubes and nitrogen-doped carbon nanotubes exhibited low, but measureable affinities for lanthanide ions in dilute nitric acid solutions (pH 3 and 6). The MWCNT exhibited much lower affinities than the K-TSP in dilute nitric acid solutions. However, the MWCNT are much more chemically stable in concentrated nitric acid solutions and, therefore, may be candidates for ion exchange in more concentrated nitric acid solutions

Hydrothermal synthesis and structural characterization of ammonium ion-templated lanthanide(III) carboxylate-phosphonates

Using N (phosphonomethyl)iminodiacetic acid (H4PMIDA), as a complexing agent, two new complexes, (NH4)La(PMIDA)(H2O)•H2O, 1 and (NH4)Yb(PMIDA), 2 have been synthesized hydrothermally. In both compounds, the metal ions are trapped in a three five-membered chelate rings by the chelating PMIDA anions giving a bi-capped trigonal prism LaO8N and capped trigonal prism YbO6N geometries for 1 and 2, respectively. The structure of 1 consists of La(PMIDA)(H2O) chelating units, linked together by the phosphonate oxygen atoms O1 and O3 to form a double chain along the c-axis. The double chains are then connected together by the bridging phosphonate oxygen O2 to form a 2D layered structure with alternating 4- and 8-membered apertures.The structure of 2 consists Yb(PMIDA) chelating units, which are connected by alternating bridging carboxylate and phosphonate groups along the [010] direction forming chains with a corrugated pattern. The third phosphonate oxygen bridges the chains together along the [001] direction to build the two-dimensional layer with 4 and 6 membered apertures in the bc plane. Under excitation of 330nm, compound 2 shows a broad emission band at λmax = 460nm, This emission is essentially in the blue luminescent region, which corresponds to ligand centered fluorescence

Strategic Design and Optimization of Inorganic Sorbents For Cesium, Strontium and Actinides

The basic science goal in this project identifies structure/affinity relationships for selected radionuclides and existing sorbents. The task will apply this knowledge to the design and synthesis of new sorbents that will exhibit increased affinity for cesium, strontium and actinide separations. The target problem focuses on the treatment of high-level nuclear wastes. The general approach can likewise be applied to nonradioactive separations