Catherine Dejoie

Learning from the past: Rare ε-Fe2O3 in the ancient black-glazed Jian (Tenmoku) wares

Ancient Jian wares are famous for their lustrous black glaze that exhibits unique colored patterns. Some striking examples include the brownish colored “Hares Fur” (HF) strips and the silvery “Oil Spot” (OS) patterns. Herein, we investigated the glaze surface of HF and OS samples using a variety of characterization methods. Contrary to the commonly accepted theory, we identified the presence of ε-Fe2O3, a rare metastable polymorph of Fe2O3 with unique magnetic properties, in both HF and OS samples. We found that surface crystals of OS samples are up to several micrometers in size and exclusively made of ε-Fe2O3. Interestingly, these ε-Fe2O3 crystals on the OS sample surface are organized in a periodic two dimensional fashion. These results shed new lights on the actual mechanisms and kinetics of polymorphous transitions of Fe2O3. Deciphering technologies behind the fabrication of ancient Jian wares can thus potentially help researchers improve the ε-Fe2O3 synthesis.

Mechanics and Dynamics of the Strain-Induced M1–M2 Structural Phase Transition in Individual VO2 Nanowires

The elastic properties and structural phase transitions of individual VO(2) nanowires were studied using an in situ push-to-pull microelectromechanical device to realize quantitative tensile analysis in a transmission electron microscope and a synchrotron X-ray microdiffraction beamline. A plateau was detected in the stress-strain curve, signifying superelasticity of the nanowire arising from the M1-M2 structural phase transition. The transition was induced and controlled by uniaxial tension. The transition dynamics were characterized by a one-dimensionally aligned domain structure with pinning and depinning of the domain walls along the nanowire. From the stress-strain dependence the Youngs moduli of the VO(2) M1 and M2 phases were estimated to be 128 ± 10 and 156 ± 10 GPa, respectively. Single pinning and depinning events of M1-M2 domain wall were observed in the superelastic regime, allowing for evaluation of the domain wall pinning potential energy. This study demonstrates a new way to investigate nanoscale mechanics and dynamics of structural phase transitions in general.

Mechanistic Studies of Water Electrolysis and Hydrogen Electro-Oxidation on High Temperature Ceria-Based Solid Oxide Electrochemical Cells

Through the use of ambient pressure X-ray photoelectron spectroscopy (APXPS) and a single-sided solid oxide electrochemical cell (SOC), we have studied the mechanism of electrocatalytic splitting of water (H2O + 2e(-) → H2 + O(2-)) and electro-oxidation of hydrogen (H2 + O(2-) → H2O + 2e(-)) at ∼700 °C in 0.5 Torr of H2/H2O on ceria (CeO2-x) electrodes. The experiments reveal a transient build-up of surface intermediates (OH(-) and Ce(3+)) and show the separation of charge at the gas-solid interface exclusively in the electrochemically active region of the SOC. During water electrolysis on ceria, the increase in surface potentials of the adsorbed OH(-) and incorporated O(2-) differ by 0.25 eV in the active regions. For hydrogen electro-oxidation on ceria, the surface concentrations of OH(-) and O(2-) shift significantly from their equilibrium values. These data suggest that the same charge transfer step (H2O + Ce(3+) <-> Ce(4+) + OH(-) + H(•)) is rate limiting in both the forward (water electrolysis) and reverse (H2 electro-oxidation) reactions. This separation of potentials reflects an induced surface dipole layer on the ceria surface and represents the effective electrochemical double layer at a gas-solid interface. The in situ XPS data and DFT calculations show that the chemical origin of the OH(-)/O(2-) potential separation resides in the reduced polarization of the Ce-OH bond due to the increase of Ce(3+) on the electrode surface. These results provide a graphical illustration of the electrochemically driven surface charge transfer processes under relevant and nonultrahigh vacuum conditions.

Role of joule heating effect and bulk-surface phases in voltage-driven metal-insulator transition in VO2 crystal

We report the characteristics of a voltage-induced metal-insulator transition (MIT) in macro-sized VO2 crystals. The square of MIT onset voltage (VCMIT2) value shows a linear dependence with the ambient temperature, suggesting that the Joule heating effect is the likely cause to the voltage-induced MIT. The combination of optical microscope images and Laue microdiffraction patterns show the simultaneous presence of a metallic phase in the bulk of the crystal with partially insulating surface layers even after the MIT occurs. A large asymmetry in the heating power just before and after the MIT reflects the sudden exchange of Joule heat to its environment.

Using a non-monochromatic microbeam for serial snapshot crystallography

The new X-ray free-electron laser source (SwissFEL) that is currently being developed at PSI will provide a broad-bandpass mode with an energy bandwidth of about 4%. By using the full energy range, a new option for structural studies of crystalline materials may become possible. The proof of concept of broad-bandpass diffraction presented here is based on Laue single-crystal microdiffraction and the experimental setup on BL12.3.2 at the Advanced Light Source in Berkeley. Diffraction patterns for 100 randomly oriented stationary crystallites of the MFI-type zeolite ZSM-5 were simulated assuming several bandwidths, and the statistical and structural results are discussed. With a 4% energy bandwidth, the number of reflection intensities measured in a single shot is significantly higher than with monochromatic radiation. Furthermore, the problem of partial reflection measurement, which is inherent to the monochromatic mode with stationary crystals, can be overcome.

Can Laue microdiffraction be used to solve and refine complex inorganic structures

The white-beam Laue diffraction experiment is an attractive alternative to the more conventional monochromatic one for single-crystal structure analysis, because it takes full advantage of the X-ray energy spectrum of a synchrotron source and requires no rotation of the crystal in the beam. Therefore, it could be used for structural characterizations under in situ or operando conditions. The potential of Laue diffraction was recognized and exploited by the protein community many years ago, and the methodology, which involved positioning and rotating the crystal in the beam, has been successfully applied to the determination of both protein and small-molecule crystal structures. Here, it is proposed that the specificities of Laue diffraction are exploited to study randomly oriented stationary microcrystals of inorganic materials. In order to determine the best strategy for collecting a reasonable quantity of data from stationary crystals, a series of simulations on four model structures for three experimental setups have been performed. It is shown that the structures of the four samples can be solved with the dual-space method in SHELX, even though the data sets are highly incomplete and much of the low-resolution part is missing. The experimental setup and data collection strategy for measuring such microcrystals have been developed on BL12.3.2 at the Advanced Light Source in Berkeley. The intensities of reflections with one and two harmonics can be extracted reliably by exploiting the tunable low-energy threshold of a Pilatus detector. In this way, the number of usable reflections can be increased from 75 to 95%. Such Laue microdiffraction data have been measured and used successfully to refine the structures of the model samples.

Unambiguous indexing of trigonal crystals from white‐beam Laue diffraction patterns: application to Dauphiné twinning and lattice stress mapping in deformed quartz

Synchrotron X-ray Laue microdiffraction is used to investigate the microstructure of deformed quartz, which has trigonal symmetry. The unambiguous indexing of a Laue diffraction pattern can only be achieved by taking the intensities of the diffraction peaks into account. The intensities are compared with theoretical structure factors after correction for the incident X-ray beam flux, X-ray beam polarization, air absorption, detector response and Lorentz factor. This allows mapping of not only the grain orientation but also the stress tensor. The method is applicable for correct orientation determination of all crystals with trigonal symmetry and is indispensable for structure refinements of such materials from Laue diffraction data.

Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal–Organic Frameworks

During nuclear waste disposal process, radioactive iodine as a fission product can be released. The widespread implementation of sustainable nuclear energy thus requires the development of efficient iodine stores that have simultaneously high capacity, stability and more importantly, storage density (and hence minimized system volume). Here, we report high I2 adsorption in a series of robust porous metal–organic materials, MFM-300(M) (M = Al, Sc, Fe, In). MFM-300(Sc) exhibits fully reversible I2 uptake of 1.54 g g–1, and its structure remains completely unperturbed upon inclusion/removal of I2. Direct observation and quantification of the adsorption, binding domains and dynamics of guest I2 molecules within these hosts have been achieved using XPS, TGA-MS, high resolution synchrotron X-ray diffraction, pair distribution function analysis, Raman, terahertz and neutron spectroscopy, coupled with density functional theory modeling. These complementary techniques reveal a comprehensive understanding of the host–I2 and I2–I2 binding interactions at a molecular level. The initial binding site of I2 in MFM-300(Sc), I2I, is located near the bridging hydroxyl group of the [ScO4(OH)2] moiety [I2I···H–O = 2.263(9) Å] with an occupancy of 0.268. I2II is located interstitially between two phenyl rings of neighboring ligand molecules [I2II···phenyl ring = 3.378(9) and 4.228(5) Å]. I2II is 4.565(2) Å from the hydroxyl group with an occupancy of 0.208. Significantly, at high I2 loading an unprecedented self-aggregation of I2 molecules into triple-helical chains within the confined nanovoids has been observed at crystallographic resolution, leading to a highly efficient packing of I2 molecules with an exceptional I2 storage density of 3.08 g cm–3 in MFM-300(Sc).

Association of indigo with zeolites for improved color stabilization.

The durability of an organic color and its resistance against external chemical agents and exposure to light can be significantly enhanced by hybridizing the natural dye with a mineral. In search for stable natural pigments, the present work focuses on the association of indigo blue with several zeolitic matrices (LTA zeolite, mordenite, MFI zeolite). The manufacturing of the hybrid pigment is tested under varying oxidizing conditions, using Raman and ultraviolet–visible (UV-Vis) spectrometric techniques. Blending indigo with MFI is shown to yield the most stable composite in all of our artificial indigo pigments. In the absence of defects and substituted cations such as aluminum in the framework of the MFI zeolite matrix, we show that matching the pore size with the dimensions of the guest indigo molecule is the key factor. The evidence for the high color stability of indigo@MFI opens a new path for modeling the stability of indigo in various alumino-silicate substrates such as in the historical Maya Blue pigment.

Elemental Topological Dirac Semimetal: α -Sn on InSb(111)

Three-dimensional (3D) topological Dirac semimetals (TDSs) are rare but important as a versatile platform for exploring exotic electronic properties and topological phase transitions. A quintessential feature of TDSs is 3D Dirac fermions associated with bulk electronic states near the Fermi level. Using angle-resolved photoemission spectroscopy, we have observed such bulk Dirac cones in epitaxially grown α-Sn films on InSb(111), the first such TDS system realized in an elemental form. First-principles calculations confirm that epitaxial strain is key to the formation of the TDS phase. A phase diagram is established that connects the 3D TDS phase through a singular point of a zero-gap semimetal phase to a topological insulator phase. The nature of the Dirac cone crosses over from 3D to 2D as the film thickness is reduced.