X-ray linear dichroic tomography of crystallographic and topological defects.

The functionality of materials is determined by their composition and microstructure, that is, the distribution and orientation of crystalline grains, grain boundaries and the defects within them. Until now, characterization techniques that map the distribution of grains, their orientation and the presence of defects have been limited to surface investigations, to spatial resolutions of a few hundred nanometres or to systems of thickness around 100 nm, thus requiring destructive sample preparation for measurements and preventing the study of system-representative volumes or the investigation of materials under operational conditions. Here we present X-ray linear dichroic orientation tomography (XL-DOT), a quantitative, non-invasive technique that allows for an intragranular and intergranular characterization of extended polycrystalline and non-crystalline materials in three dimensions.

XPS investigation of the SEI formed on LGPS and LAGP with metallic lithium.

X-ray photoelectron spectroscopy (XPS) techniques have proven to be powerful tools for the characterisation of the solid electrolyte interphase (SEI) formed between the anode and solid electrolyte (SE) in solid-state batteries. XPS offers access to time and operational condition-resolved information on the SEI's chemical composition in the absence of destructive sample preparation. Here we present a Virtual Electrode Plating XPS (VEP-XPS) investigation of the composition and stability of the SEI formed between lithium metal and two different solid electrolytes: LiGePS (LGPS) and LiAlGe(PO) (LAGP).

Alumina-Supported NiMo Hydrotreating Catalysts-Aspects of 3D Structure, Synthesis, and Activity.

Preparation conditions have a vital effect on the structure of alumina-supported hydrodesulfurization (HDS) catalysts. To explore this effect, we prepared two NiMoS/AlO catalyst samples with the same target composition using different chemical sources and characterizing the oxidic NiMo precursors and sulfided and spent catalysts to understand the influence of catalyst structure on performance. The sample prepared from ammonium heptamolybdate and nickel nitrate (sample A) contains Mo in the oxidic precursor predominantly in tetrahedral coordination in the form of crystalline domains, which show low reducibility and strong metal-support interactions.

Environmental control for X-ray nanotomography.

The acquisition speed and spatial resolution of X-ray nanotomography have continuously improved over the last decades. Coherent diffraction-based techniques breach the 10 nm resolution barrier frequently and thus pose stringent demands on sample positioning accuracy and stability. At the same time there is an increasing desire to accommodate in situ or operando measurements.

Mechanical adaptation of brachiopod shells via hydration-induced structural changes.

The function-optimized properties of biominerals arise from the hierarchical organization of primary building blocks. Alteration of properties in response to environmental stresses generally involves time-intensive processes of resorption and reprecipitation of mineral in the underlying organic scaffold. Here, we report that the load-bearing shells of the brachiopod Discinisca tenuis are an exception to this process.

Characterising lithium-ion electrolytes via operando Raman microspectroscopy.

Knowledge of electrolyte transport and thermodynamic properties in Li-ion and beyond Li-ion technologies is vital for their continued development and success. Here, we present a method for fully characterising electrolyte systems. By measuring the electrolyte concentration gradient over time via operando Raman microspectroscopy, in tandem with potentiostatic electrochemical impedance spectroscopy, the Fickian "apparent" diffusion coefficient, transference number, thermodynamic factor, ionic conductivity and resistance of charge-transfer were quantified within a single experimental setup.

Sparse ab initio x-ray transmission spectrotomography for nanoscopic compositional analysis of functional materials.

The performance of functional materials is either driven or limited by nanoscopic heterogeneities distributed throughout the material's volume. To better our understanding of these materials, we need characterization tools that allow us to determine the nature and distribution of these heterogeneities in their native geometry in 3D. Here, we introduce a method based on x-ray near-edge spectroscopy, ptychographic x-ray computed nanotomography, and sparsity techniques.

Visualizing plating-induced cracking in lithium-anode solid-electrolyte cells.

Lithium dendrite (filament) propagation through ceramic electrolytes, leading to short circuits at high rates of charge, is one of the greatest barriers to realizing high-energy-density all-solid-state lithium-anode batteries. Utilizing in situ X-ray computed tomography coupled with spatially mapped X-ray diffraction, the propagation of cracks and the propagation of lithium dendrites through the solid electrolyte have been tracked in a Li/LiPSCl/Li cell as a function of the charge passed. On plating, cracking initiates with spallation, conical 'pothole'-like cracks that form in the ceramic electrolyte near the surface with the plated electrode.

Spatio-Chemical Heterogeneity of Defect-Engineered Metal-Organic Framework Crystals Revealed by Full-Field Tomographic X-ray Absorption Spectroscopy.

The introduction of structural defects in metal-organic frameworks (MOFs), often achieved through the fractional use of defective linkers, is emerging as a means to refine the properties of existing MOFs. These linkers, missing coordination fragments, create unsaturated framework nodes that may alter the properties of the MOF. A property-targeted utilization of this approach demands an understanding of the structure of the defect-engineered MOF.

Nanoscale crystal grain characterization linear polarization X-ray ptychography.

X-ray linear dichroism and X-ray birefringence microscopy are yet to be fully utilized as instruments in the microstructural characterization of crystalline materials. Here, we demonstrate analyser-free X-ray linear dichroism microscopy using spectroscopic hard X-ray ptychography. First experiments enabled a spectroscopic and microstructural characterisation of polycrystalline vanadium pentoxide on the nanoscale, outside of diffraction-contrast based methods.

Ptychographic X-ray tomography reveals additive zoning in nanocomposite single crystals.

Single crystals containing nanoparticles represent a unique class of nanocomposites whose properties are defined by both their compositions and the structural organization of the dispersed phase in the crystalline host. Yet, there is still a poor understanding of the relationship between the synthesis conditions and the structures of these materials. Here ptychographic X-ray computed tomography is used to visualize the three-dimensional structures of two nanocomposite crystals - single crystals of calcite occluding diblock copolymer worms and vesicles.

Hierarchical Structure of NiMo Hydrodesulfurization Catalysts Determined by Ptychographic X-Ray Computed Tomography.

Hydrodesulphurization, the removal of sulphur from crude oils, is an essential catalytic process in the petroleum industry safeguarding the production of clean hydrocarbons. Sulphur removal is critical for the functionality of downstream processes and vital to the elimination of environmental pollutants. The effectiveness of such an endeavour is among other factors determined by the structural arrangement of the heterogeneous catalyst.

A lathe system for micrometre-sized cylindrical sample preparation at room and cryogenic temperatures.

A simple two-spindle based lathe system for the preparation of cylindrical samples intended for X-ray tomography is presented. The setup can operate at room temperature as well as under cryogenic conditions, allowing the preparation of samples down to 20 and 50 µm in diameter, respectively, within minutes. Case studies are presented involving the preparation of a brittle biomineral brachiopod shell and cryogenically fixed soft brain tissue, and their examination by means of ptychographic X-ray computed tomography reveals the preparation method to be mainly free from causing artefacts.

Super-Resolution Microscopy Reveals Shape and Distribution of Dislocations in Single-Crystal Nanocomposites.

With their potential to offer new properties, single crystals containing nanoparticles provide an attractive class of nanocomposite materials. However, to fully profit from these, it is essential that we can characterise their 3D structures, identifying the locations of individual nanoparticles, and the defects present within the host crystals. Using calcite crystals containing quantum dots as a model system, we here use 3D stochastic optical reconstruction microscopy (STORM) to locate the positions of the nanoparticles within the host crystal.

The Link between ZSM-5 Zeolite Crystallization and Mesopore Formation by Leaching.

Acid or base leaching are well-established tools in the synthesis of mesoporous zeolites. Previous studies suggest an inherent link between the structure-property relationship of mesoporous zeolites, that is, chemical resistance, pore diameter and distribution, with zeolite synthesis or crystallization conditions. The exact nature and/or origin of this link is currently however, poorly established.

Visualization of the effect of additives on the nanostructures of individual bio-inspired calcite crystals.

Soluble additives provide a versatile strategy for controlling crystallization processes, enabling selection of properties including crystal sizes, morphologies, and structures. The additive species can also be incorporated within the crystal lattice, leading for example to enhanced mechanical properties. However, while many techniques are available for analyzing particle shape and structure, it remains challenging to characterize the structural inhomogeneities and defects introduced into individual crystals by these additives, where these govern many important material properties.

X-ray Fourier ptychography.

To a large extent, the performance of imaging systems is determined by their objectives, which affect properties as varied as collection efficiency, resolving power, and image distortions. Such limitations can be addressed by so-called aperture synthesis, a technique used, for instance, in radar, astronomy, and, increasingly, microscopy. Here, we apply such techniques to x-ray imaging and demonstrate how Fourier ptychography can be used at transmission x-ray microscopes to increase resolution, provide quantitative absorption and phase contrast, and allow for corrections of lens aberrations.

Correlated X-Ray 3D Ptychography and Diffraction Microscopy Visualize Links between Morphology and Crystal Structure of Lithium-Rich Cathode Materials.

The search for higher performance, improved safety, and lifetime of lithium-ion batteries relies on the understanding of degradation mechanisms. Complementary to methods and studies on primary particles or crystalline structure on bulk materials, here we use spatially correlated ptychographic X-ray computed nanotomography with a 35 nm resolution and scanning X-ray diffraction microscopy with 1 μm resolution to visualize in 3D the hidden morphological and structural degradation processes in individual secondary particles of lithium-rich nickel, cobalt, and manganese oxides. From comparative examination of pristine and cycled particles, we suggest that morphological degradation could have radial dependency and secondary particle size dependency.

Heavy atom labeling enables silanol defect visualization in silicalite-1 crystals.

Using heavy-atom labeling in conjunction with electron microscopy, we here visualize the distribution of point defects, i.e. internal silanol groups, in silicalite-1 zeolites at the single crystal level.

Enzymatically-controlled biomimetic synthesis of titania/protein hybrid thin films.

Although it is widely recognised that enzymes play a significant role in sculpting complex silica skeletons in marine sponges, the potential for exploiting enzymes in materials synthesis has not yet been fully harnessed. In this work we show that the digestive enzyme papain can self-assemble into monolayers on oxide surfaces, where they then drive the formation of crystalline titanium dioxide nanoparticles. This dual functionality of thin film formation and mineralization promotion has the potential to enable the construction of hierarchical inorganic/organic structures in the form of continuous amorphous titania/protein films which can be refined to 93% anatase post annealing.

Amino Acid Assisted Incorporation of Dye Molecules within Calcite Crystals.

Biomineralisation processes invariably occur in the presence of multiple organic additives, which act in combination to give exceptional control over structures and properties. However, few synthetic studies have investigated the cooperative effects of soluble additives. This work addresses this challenge and focuses on the combined effects of amino acids and coloured dye molecules.

A three-dimensional view of structural changes caused by deactivation of fluid catalytic cracking catalysts.

Since its commercial introduction three-quarters of a century ago, fluid catalytic cracking has been one of the most important conversion processes in the petroleum industry. In this process, porous composites composed of zeolite and clay crack the heavy fractions in crude oil into transportation fuel and petrochemical feedstocks. Yet, over time the catalytic activity of these composite particles decreases.