Paul Barnes

Dynamic X‐Ray Diffraction Computed Tomography Reveals Real‐Time Insight into Catalyst Active Phase Evolution

Metals and metal oxides anchored to porous support materials are widely used as heterogeneous catalysts in a number of important industrial chemical processes. These catalysts owe their activity to the formation of unique metal/metal oxide support interactions, typically resulting in highly dispersed actives stabilized in a particular electronic or coordination state. They are employed in fixed-bed reactors as extruded or pelletized millimeter-sized “catalyst bodies” minimizing pressure drops along the length of the reactor. Since the efficiency of the whole catalytic system depends on the behavior and efficiency of the catalyst body per se, its design has very great importance. Crucial to this design is an understanding of the factors which influence the distribution and nature of the active phase during preparation. The type of desired distribution is very much dependant on catalytic process and required products; for example, an egg-shell distribution (as opposed to uniform, egg-white, or egg-yolk), where the active phase is located at the edges of the catalyst body, can be favored if the product forms readily.

Active phase evolution in single Ni/Al2O3 methanation catalyst bodies studied in real time using combined μ-XRD-CT and μ-absorption-CT

A combination of synchrotron μ-XRD-CT and μ-absorption-CT (CT = computed tomography) is demonstrated, providing a unique insight into the solid state changes occurring from within crystalline materials. Specifically, we examine here the solid state changes that occur in a millimetre-sized Ni/γ-Al2O3 catalyst body in both 2D and 3D during calcination and CO methanation for the first time. The combination provides a unique insight into the spatial phase distribution of these materials and how these evolve via a series of solid state transformation processes. For example, initially, two Ni-ethylenediamine (en) complexes were observed on the impregnated and dried body; a hydrated and non-hydrated form, which 2D scans reveal possess an egg-shell and egg-yolk distribution, respectively. Furthermore, the μ-XRD data were of sufficient quality so as to be able to reveal that the particles within the ‘egg-shell’ were larger (∼35 nm) than those of the ‘egg-yolk’ (∼19 nm) and that there were more of them. On calcination, both precursors collapsed, yielding metallic fcc Ni particles with a surprisingly uniform average size distribution over the catalyst (∼4 nm). However, a comparison of the scattering at different stages of the experiment suggested that the crystalline structure of some of the Ni remained diffraction ‘silent’. Calcination in oxygen lead to both Ni oxidation and particle sintering, mainly at the exterior, which on pre-reaction reduction (in H2) yielded again fcc Ni particles (∼4 nm interior, ∼6 nm exterior) with a significant reduction in the amorphous Ni component. The catalyst proved active for CO methanation and, during 2 h time on-stream, no change in the structure composition or shape was observed, leading us to conclude that nano-sized fcc Ni particles on γ-Al2O3 are the active component in CO methanation. This work therefore demonstrates both the power of spatially resolved μ-XRD-CT/μ-absorption-CT measurement of catalytic systems and its advantage over more ‘traditional’ single point studies on small sieve fractions.

Tomographic Energy Dispersive Diffraction Imaging To Study the Genesis of Ni Nanoparticles in 3D within γ-Al2O3 Catalyst Bodies

Tomographic energy dispersive diffraction imaging (TEDDI) is a recently developed synchrotron-based characterization technique used to obtain spatially resolved X-ray diffraction and fluorescence information in a noninvasive manner. With the use of a synchrotron beam, three-dimensional (3D) information can be conveniently obtained on the elemental composition and related crystalline phases of the interior of a material. In this work, we show for the first time its application to characterize the structure of a heterogeneous catalyst body in situ during thermal treatment. Ni/gamma-Al(2)O(3) hydrogenation catalyst bodies have been chosen as the system of study. As a first example, the heat treatment in N(2) of a [Ni(en)(3)](NO(3))(2)/gamma-Al(2)O(3) catalyst body has been studied. In this case, the crystalline [Ni(en)(3)](NO(3))(2) precursor was detected in an egg-shell distribution, and its decomposition to form metallic Ni crystallites of around 5 nm was imaged. In the second example, the heat treatment in N(2) of a [Ni(en)(H(2)O)(4)]Cl(2)/gamma-Al(2)O(3) catalyst body was followed. The initial [Ni(en)(H(2)O)(4)]Cl(2) precursor was uniformly distributed within the catalyst body as an amorphous material and was decomposed to form metallic Ni crystallites of around 30 nm with a uniform distribution. TEDDI also revealed that the decomposition of [Ni(en)(H(2)O)(4)]Cl(2) takes place via two intermediate crystalline structures. The first one, which appears at around 180 degrees C, is related to the restructuring of the Ni precursor on the alumina surface; the second one, assigned to the formation of a limited amount of Ni(3)C, is observed at 290 degrees C.

Thermal decomposition of ettringite Ca6[Al(OH)6]2(SO4)3·26H2O

The thermal decomposition of ettringite in the presence of water and impurity gypsum has been observed by energy-dispersive synchrotron X-ray diffraction and FTIR spectroscopy. The decomposition occurs rapidly at 114 °C to produce a monosulfate, with 0.96 nm interlayer spacing, and bassanite. The thermal expansion of ettringite from 70 to 110 °C is 42 × 10–6 K–1 in the a direction and 22 × 10–6 K–1 in the c direction. The gypsum acts as a transient intermediate in the decomposition. The mechanism of this rapid decomposition is discussed.

High-throughput continuous hydrothermal flow synthesis of Zn-Ce oxides: unprecedented solubility of Zn in the nanoparticle fluorite lattice

High-throughput continuous hydrothermal flow synthesis has been used as a rapid and efficient synthetic route to produce a range of crystalline nanopowders in the Ce–Zn oxide binary system. High-resolution powder X-ray diffraction data were obtained for both as-prepared and heat-treated (850°C for 10 h in air) samples using the new robotic beamline I11, located at Diamond Light Source. The influence of the sample composition on the crystal structure and on the optical and physical properties was studied. All the nanomaterials were characterized using Raman spectroscopy, UV–visible spectrophotometry, Brunauer–Emmett–Teller surface area and elemental analysis (via energy-dispersive X-ray spectroscopy). Initially, for ‘as-prepared’ Ce1−xZnxOy, a phase-pure cerium oxide (fluorite) structure was obtained for nominal values of x=0.1 and 0.2. Biphasic mixtures were obtained for nominal values of x in the range of 0.3–0.9 (inclusive). High-resolution transmission electron microscopy images revealed that the phase-pure nano-CeO2 (x=0) consisted of ca 3.7 nm well-defined nanoparticles. The nanomaterials produced herein generally had high surface areas (greater than 150 m2 g−1) and possessed combinations of particle properties (e.g. bandgap, crystallinity, size, etc.) that were unobtainable or difficult to achieve by other more conventional synthetic methods.

In-situ hydration studies using multi-angle energy-dispersive diffraction.

A new diffractometer has been built with which energy-dispersive diffraction patterns can be collected simultaneously at different angles. The first use of this system for dynamic (time-resolved) studies--the hydration of cements under various conditions--is reported. It is found that the optimization available with a three-element detector system enables collection of high-quality patterns over a much wider and more effective range of reciprocal space, and this yields improved and new information on the hydration processes.

Rapid whole-rock mineral analysis and composition mapping by synchrotron X-ray diffraction

We show that 25–140 keV X-rays from high-brilliance synchrotron sources can penetrate through 25 mm of intact rock. Powder diffraction patterns are obtained rapidly by energy-dispersive detection. Data acquisition time is reduced by a large factor (say 102–103) compared with standard laboratory powder diffraction methods. Data are presented on sedimentary rock cores and mineral standards. Full-pattern fitting is used for quantitative modal analysis of the composition. Using acquisition times of only 20 s for each pattern, we show the feasibility of line traverse (conveyor-belt) X-ray diffraction analysis and compositional tomography with sub-millimeter resolution.

A new approach to synchrotron energy-dispersive X-ray diffraction computed tomography

A new data collection strategy for performing synchrotron energy-dispersive X-ray diffraction computed tomography has been devised. This method is analogous to angle-dispersive X-ray diffraction whose diffraction signal originates from a line formed by intersection of the incident X-ray beam and the sample. Energy resolution is preserved by using a collimator which defines a small sampling voxel. This voxel is translated in a series of parallel straight lines covering the whole sample and the operation is repeated at different rotation angles, thus generating one diffraction pattern per translation and rotation step. The method has been tested by imaging a specially designed phantom object, devised to be a demanding validator for X-ray diffraction imaging. The relative strengths and weaknesses of the method have been analysed with respect to the classic angle-dispersive technique. The reconstruction accuracy of the method is good, although an absorption correction is required for lower energy diffraction because of the large path lengths involved. The spatial resolution is only limited to the width of the scanning beam owing to the novel collection strategy. The current temporal resolution is poor, with a scan taking several hours. The method is best suited to studying large objects (e.g. for engineering and materials science applications) because it does not suffer from diffraction peak broadening effects irrespective of the sample size, in contrast to the angle-dispersive case.

A synchrotron tomographic energy-dispersive diffraction imaging study of the aerospace alloy Ti 6246

A titanium alloy sample (#6246) containing a linear friction weld has been imaged nondestructively using tomographic energy-dispersive diffraction imaging (TEDDI). The diffraction patterns measured at each point of the TEDDI image permitted identification of the material and phases present (±5%). The image also showed the preferred orientation and size–strain distribution present within the sample without the need for any further sample preparation. The preferred orientation was observed in clusters with average dimensions very similar to the experimental spatial resolution (400 µm). The length scales and preferred orientation distributions were consistent with orientation imaging microscopy measurements made by Szczepanski, Jha, Larsen & Jones [Metall. Mater. Trans. A (2008), 39, 2841–2851] where the microstructure development was linked to the grain growth of the parent material. The use of a high-energy X-ray distribution (30–80 keV) in the incident beam reduced systematic errors due to the source profile, sample and air absorption. The TEDDI data from each voxel were reduced to an angle-dispersive form and Rietveld refined to a mean χ2 of 1.4. The mean lattice parameter error (δd/d) ranged from ∼10−4 for the highly crystalline regions to ∼10−3 for regions of very strong preferred orientation and internal strain. The March–Dollase preferred orientation errors refined to an average value of ±2%. A 100% correlation between observed fluorescence and diffraction peak broadening was observed, providing further evidence for vicinal strain broadening.

Direct correlation between ferrite microstructure and electrical resistivity

Variations in the composition and microstructure of Mn-Zn soft ferrites have been directly correlated with spatial variations in electrical resistivity, which were both observed to occur on a length scale of approximately 500 μm. Tomographic energy dispersive diffraction imaging (TEDDI) was used to determine the nonsystematic change in the lattice parameter across the sample volume (8.48±0.05 A) at a spatial resolution of 50 μm. We have used a microprobe contact technique to measure the local electrical resistivity (∼35 Ω cm) and density functional theory to model the band structure. The band structure calculations directly utilized the experimentally measured lattice parameters from the TEDDI measurements and were in good agreement with the measured resistivity. The mean band gap shrinkage was found to be 0.02 eV. This value for Eg was found to account well for the observed 10−20 Ω cm resistivity variations.