Showing papers by "Tolek Tyliszczak published in 2014"

Chemical composition mapping with nanometre resolution by soft X-ray microscopy

Abstract: A soft X-ray ptychography approach can now image 5-nm-sized objects. Chemical component distributions in the delithiation of LiFePO4 nanoplates — a process relevant for energy storage — links structural defects to chemical phase propagation.

Current-induced transition from particle-by-particle to concurrent intercalation in phase-separating battery electrodes

Abstract: Many battery electrodes contain ensembles of nanoparticles that phase-separate on (de)intercalation. In such electrodes, the fraction of actively intercalating particles directly impacts cycle life: a vanishing population concentrates the current in a small number of particles, leading to current hotspots. Reports of the active particle population in the phase-separating electrode lithium iron phosphate (LiFePO4; LFP) vary widely, ranging from near 0% (particle-by-particle) to 100% (concurrent intercalation). Using synchrotron-based X-ray microscopy, we probed the individual state-of-charge for over 3,000 LFP particles. We observed that the active population depends strongly on the cycling current, exhibiting particle-by-particle-like behaviour at low rates and increasingly concurrent behaviour at high rates, consistent with our phase-field porous electrode simulations. Contrary to intuition, the current density, or current per active internal surface area, is nearly invariant with the global electrode cycling rate. Rather, the electrode accommodates higher current by increasing the active particle population. This behaviour results from thermodynamic transformation barriers in LFP, and such a phenomenon probably extends to other phase-separating battery materials. We propose that modifying the transformation barrier and exchange current density can increase the active population and thus the current homogeneity. This could introduce new paradigms to enhance the cycle life of phase-separating battery electrodes.

Influence of Pyrazolate vs N‑Heterocyclic Carbene Ligands on the Slow Magnetic Relaxation of Homoleptic Trischelate Lanthanide(III) and Uranium(III) Complexes

Abstract: Two isostructural series of trigonal prismatic complexes, M(BpMe)3 and M(BcMe)3 (M = Y, Tb, Dy, Ho, Er, U; [BpMe]− = dihydrobis(methypyrazolyl)borate; [BcMe]− = dihydrobis(methylimidazolyl)borate) are synthesized and fully characterized to examine the influence of ligand donor strength on slow magnetic relaxation. Investigation of the dynamic magnetic properties reveals that the oblate electron density distributions of the Tb3+, Dy3+, and U3+ metal ions within the axial ligand field lead to slow relaxation upon application of a small dc magnetic field. Significantly, the magnetization relaxation is orders of magnitude slower for the N-heterocyclic carbene complexes, M(BcMe)3, than for the isomeric pyrazolate complexes, M(BpMe)3. Further, investigation of magnetically dilute samples containing 11–14 mol % of Tb3+, Dy3+, or U3+ within the corresponding Y3+ complex matrix reveals thermally activated relaxation is favored for the M(BcMe)3 complexes, even when dipolar interactions are largely absent. Notably, ...

Evidence for interstellar origin of seven dust particles collected by the Stardust spacecraft

Abstract: Seven particles captured by the Stardust Interstellar Dust Collector and returned to Earth for laboratory analysis have features consistent with an origin in the contemporary interstellar dust stream. More than 50 spacecraft debris particles were also identified. The interstellar dust candidates are readily distinguished from debris impacts on the basis of elemental composition and/or impact trajectory. The seven candidate interstellar particles are diverse in elemental composition, crystal structure, and size. The presence of crystalline grains and multiple iron-bearing phases, including sulfide, in some particles indicates that individual interstellar particles diverge from any one representative model of interstellar dust inferred from astronomical observations and theory.

New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory

Abstract: Evidence for metal–carbon orbital mixing in thorocene and uranocene was determined from DFT calculations and carbon K-edge X-ray absorption spectra (XAS) collected with a scanning transmission X-ray microscope (STXM). Both the experimental and computational results showed that the 5f orbitals engaged in significant δ-type mixing with the C8H82− ligands, which increased as the 5f orbitals dropped in energy on moving from Th4+ to U4+. The first experimental evidence for extensive ϕ-orbital interactions has been provided by the C K-edge XAS analysis of thorocene; however, ϕ-type covalency in uranocene was negligible. The results highlighted two contrasting trends in orbital mixing from one pair of highly symmetric molecules, and showed that covalency does not increase uniformly for different molecular orbital interactions with later actinides.

Comparison of x-ray absorption spectra between water and ice: new ice data with low pre-edge absorption cross-section.

Abstract: The effect of crystal growth conditions on the O K-edge x-ray absorption spectra of ice is investigated through detailed analysis of the spectral features. The amount of ice defects is found to be minimized on hydrophobic surfaces, such as BaF2(111), with low concentration of nucleation centers. This is manifested through a reduction of the absorption cross-section at 535 eV, which is associated with distorted hydrogen bonds. Furthermore, a connection is made between the observed increase in spectral intensity between 544 and 548 eV and high-symmetry points in the electronic band structure, suggesting a more extended hydrogen-bond network as compared to ices prepared differently. The spectral differences for various ice preparations are compared to the temperature dependence of spectra of liquid water upon supercooling. A double-peak feature in the absorption cross-section between 540 and 543 eV is identified as a characteristic of the crystalline phase. The connection to the interpretation of the liquid phase O K-edge x-ray absorption spectrum is extensively discussed.

Oxidation of magnetite(100) to hematite observed by in situ spectroscopy and microscopy

Abstract: We study where and how hematite (α-Fe2O3) nucleates and grows during the oxidation of magnetite(100) single crystals. Hematite inclusions grow along ⟨110⟩ directions of the magnetite (Fe3O4), leading to a biaxial array of hematite slabs in an electrically conducting matrix of magnetite. The slab arrays form in both bulk single crystals and thin films of magnetite. Atomic force microscopy reveals that the surface growth of magnetite that accompanies hematite formation is faster adjacent to the hematite slabs. In situ X-ray photoelectron and X-ray absorption spectroscopies at 600 °C in an oxygen environment reveal that the conversion of the Fe2+ in magnetite to Fe3+ in hematite occurs without the formation of the metastable phase maghemite (γ-Fe2O3). We offer an explanation of why Fe3O4(100) oxidizes faster than Fe3O4(111).

Ubiquitous Presence of Fe(II) in Aquatic Colloids and Its Association with Organic Carbon

Abstract: Despite being thermodynamically less stable, small ferrous colloids (60 nm to 3 μm in diameter) remain an important component of the biogeochemical cycle at the Earth’s surface, yet their composition and structure and the reasons for their persistence are still poorly understood. Here we use X-ray-based Fe L-edge and carbon K-edge spectromicroscopy to address the speciation and organic–mineral associations of ferrous, ferric, and Fe-poor particles collected from sampling sites in both marine and freshwater environments. We show that Fe(II)-rich phases are prevalent throughout different aquatic regimes yet exhibit a high degree of chemical heterogeneity. Furthermore, we show that Fe-rich particles show strong associations with organic carbon. The observed association of Fe(II) particles with carboxamide functional groups suggests a possible microbial role in the preservation of Fe(II). These finding have significant implications for the behavior of Fe(II) colloids in oxygenated waters, and their role in different aquatic biogeochemical processes.

Sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy setup for pulsed and constant wave X-ray light sources

Abstract: An apparatus for sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy studies with pulsed and constant wave X-ray light sources is presented. A differentially pumped hemispherical electron analyzer is equipped with a delay-line detector that simultaneously records the position and arrival time of every single electron at the exit aperture of the hemisphere with ~0.1 mm spatial resolution and ~150 ps temporal accuracy. The kinetic energies of the photoelectrons are encoded in the hit positions along the dispersive axis of the two-dimensional detector. Pump-probe time-delays are provided by the electron arrival times relative to the pump pulse timing. An average time-resolution of (780 ± 20) ps (FWHM) is demonstrated for a hemisphere pass energy E(p) = 150 eV and an electron kinetic energy range KE = 503-508 eV. The time-resolution of the setup is limited by the electron time-of-flight (TOF) spread related to the electron trajectory distribution within the analyzer hemisphere and within the electrostatic lens system that images the interaction volume onto the hemisphere entrance slit. The TOF spread for electrons with KE = 430 eV varies between ~9 ns at a pass energy of 50 eV and ~1 ns at pass energies between 200 eV and 400 eV. The correlation between the retarding ratio and the TOF spread is evaluated by means of both analytical descriptions of the electron trajectories within the analyzer hemisphere and computer simulations of the entire trajectories including the electrostatic lens system. In agreement with previous studies, we find that the by far dominant contribution to the TOF spread is acquired within the hemisphere. However, both experiment and computer simulations show that the lens system indirectly affects the time resolution of the setup to a significant extent by inducing a strong dependence of the angular spread of electron trajectories entering the hemisphere on the retarding ratio. The scaling of the angular spread with the retarding ratio can be well approximated by applying Liouville's theorem of constant emittance to the electron trajectories inside the lens system. The performance of the setup is demonstrated by characterizing the laser fluence-dependent transient surface photovoltage response of a laser-excited Si(100) sample.

Toward equatorial planarity about uranyl: synthesis and structure of tridentate nitrogen-donor {UO2}2+ complexes.

Abstract: The reaction of UO2Cl2·3THF with the tridentate nitrogen donor ligand 2,6-bis(2-benzimidazolyl)pyridine (H2BBP) in pyridine leads to the formation of three different complexes: [(UO2)(H2BBP)Cl2] (1), [(UO)2(HBBP)(Py)Cl] (2), and [(UO2)(BBP)(Py)2] (3) after successive deprotonation of H2BBP with a strong base. Crystallographic determination of 1–3 reveals that increased charge through ligand deprotonation and displacement of chloride leads to equatorial planarity about uranyl as well as a more compact overall coordination geometry. Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectra of 1–3 at the U-4d edges have been recorded using a soft X-ray Scanning Transmission X-ray Microscope (STXM) and reveal the uranium 4d5/2 and 4d3/2 transitions at energies associated with uranium in the hexavalent oxidation state. First-principles Density Functional Theory (DFT) electronic structure calculations for the complexes have been performed to determine and validate the coordination characteristics, which corres...

Synthesis and characterization of eight compounds of the MU8Q17 family: ScU8S17, CoU8S17, NiU8S17, TiU8Se17, VU8Se17, CrU8Se17, CoU8Se17, and NiU8Se17.

Abstract: The solid-state MU8Q17 compounds ScU8S17, CoU8S17, NiU8S17, TiU8Se17, VU8Se17, CrU8Se17, CoU8Se17, and NiU8Se17 were synthesized from the reactions of the elements at 1173 or 1123 K. These isostructural compounds crystallize in space group C2h3 - C2/m of the monoclinic system in the CrU8S17 structure type. X-ray absorption near-edge structure spectroscopic studies of ScU8S17 indicate that it contains Sc3+, and hence charge balance is achieved with a composition that includes U3+ as well as U4+. The other compounds charge balance with M2+ and U4+. Magnetic susceptibility measurements on ScU8S17 indicate antiferromagnetic couplings and a highly reduced effective magnetic moment. Ab Initio calculations find the compound to be metallic. Surprisingly, the Sc–S distances are actually longer than all the other M–S interactions, even though the ionic radii of Sc3+, low-spin Cr2+, and Ni2+ are similar.

Fast chirality reversal of the magnetic vortex by electric current

Abstract: The possibility of high-density information encoding in magnetic materials by topologically stable inhomogeneous magnetization configurations such as domain walls, skyrmions, and vortices has motivated intense research into mechanisms enabling their control and detection. While the uniform magnetization states can be efficiently controlled by electric current using magnetic multilayer structures, this approach has proven much more difficult to implement for inhomogeneous states. Here, we report direct observation of fast reversal of magnetic vortex by electric current in a simple planar structure based on a bilayer of spin Hall material Pt with a single microscopic ferromagnetic disk contacted by asymmetric electrodes. The reversal is enabled by a combination of the chiral Oersted field and spin current generated by the nonuniform current distribution in Pt. Our results provide a route for the efficient control of inhomogeneous magnetization configurations by electric current.

Double cation formation from the Photo-Fragmentation of the closo-Carboranes

Abstract: Time-of-flight mass analysis with multi-stop coincidence detection has been used to study the multi-cation ionic fragmentation via fission of three isomeric carborane icosahedral cage compounds closo-1,2-orthocarborane, closo-1,7-metacarborane, closo-1,12-paracarborane (C2B10H12) following inner-shell excitation at or above the B is regime. Photoelectron-photoion-photoion coincidence (PEPIPICO) spectroscopy was used to study the dominant fission routes in the core level excitation regime. Series of ion pairs are identified, where asymmetric fission dominates, leading to ion pairs of different mass. The fragmentation yields and charge separation mass spectra of all three isomers are generally quite similar in that the ion pairs (H+, Y+), Y-11(+)), and (Y-3(+), Y-9(+)) dominate, where denotes the mass region from B+ to CH. Slight differences are observed at the B 1s-threshold, where the H+ and BH2+/CH+ ion pairs dominate for ortho-and metacarborane, while (Y+, Y-11(+)) ion pairs dominate the multi-photofragment ion yield of paracarborane. These similarities and distinct differences in charge separation are discussed by considering the energetics of these three major species of ion pairs, as well as charge distributions in closo-carboranes and charge distributions in the carborane cage. It is shown that product formation via charge separation is driven by electronic relaxation, so that the lowest energy products are not necessarily formed.

Final Reports of the Stardust ISPE: Seven Probable Interstellar Dust Particles

Abstract: The Stardust spacecraft carried the first spaceborne collector specifically designed to capture and return a sample of contemporary interstellar dust to terrestrial laboratories for analysis [1]. The collector was exposed to the interstellar dust stream in two periods in 2000 and 2002 with a total exposure of approximately 1.8 10(exp 6) square meters sec. Approximately 85% of the collector consisted of aerogel, and the remainder consisted of Al foils. The Stardust Interstellar Preliminary Examination (ISPE) was a consortiumbased effort to characterize the collection in sufficient detail to enable future investigators to make informed sample requests. Among the questions to be answered were these: How many impacts are consistent in their characteristics with interstellar dust, with interplanetary dust, and with secondary ejecta from impacts on the spacecraft? Are the materials amorphous or crystalline? Are organics detectable? An additional goal of the ISPE was to develop or refine the techniques for preparation, analysis, and curation of these tiny samples, expected to be approximately 1 picogram or smaller, roughly three orders of magnitude smaller in mass than the samples in other small particle collections in NASA's collections - the cometary samples returned by Stardust, and the collection of Interplanetary Dust Particles collected in the stratosphere.

Synthesis and Characterization of Eight Compounds of the MU8Q17 Family: ScU8S17, CoU8S17, NiU8S17, TiU8Se17, VU8Se17, CrU8Se17, CoU8Se17, and NiU8Se17.

Abstract: Single crystals of the title compounds are synthesized by solid state reactions of the elements in an ACl flux (A: Cs, K, Rb) (Ar, silica tubes, 1073—1123 K, 96—168 h).