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Abstract: It is shown that higher order Laue zone (HOLZ) rings in high energy electron diffraction are specific to individual columns of atoms, and show different strengths, structure and radii for different atom columns along the same projection in a structure. An atomic resolution 4-dimensional STEM dataset is recorded from a <110> direction in a perovskite trilayer, where only the central LaFeO3 layer should show a period doubling that gives rise to an extra HOLZ ring. Careful comparison between experiment and multislice simulations is used to understand the origins of all features in the patterns. A strong HOLZ ring is seen for the La-O columns, indicating strong La position modulation along this direction, whereas a weaker ring is seen along the O columns, and a very weak ring is seen along the Fe columns. This demonstrates that atomic resolution HOLZ-STEM is a feasible method for investigating the 3D periodicity of crystalline materials with atomic resolution.

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Abstract: We induce and study reactions of polyoxometalate (POM) molecules, [PW12O40]3− (Keggin) and [P2W18O62]6− (Wells–Dawson), at the single-molecule level. Several identical carbon nanotubes aligned side by side within a bundle provided a platform for spatiotemporally resolved imaging of ca. 100 molecules encapsulated within the nanotubes by transmission electron microscopy (TEM). Due to the entrapment of POM molecules their proximity to one another is effectively controlled, limiting molecular motion in two dimensions but leaving the third dimension available for intermolecular reactions between pairs of neighbouring molecules. By coupling the information gained from high resolution structural and kinetics experiments via the variation of key imaging parameters in the TEM, we shed light on the reaction mechanism. The dissociation of W–O bonds, a key initial step of POM reactions, is revealed to be reversible by the kinetic analysis, followed by an irreversible bonding of POM molecules to their nearest neighbours, leading to a continuous tungsten oxide nanowire, which subsequently transforms into amorphous tungsten-rich clusters due to progressive loss of oxygen atoms. The overall intermolecular reaction can therefore be described as a step-wise reductive polycondensation of POM molecules, via an intermediate state of an oxide nanowire. Kinetic analysis enabled by controlled variation of the electron flux in TEM revealed the reaction to be highly flux-dependent, which leads to reaction rates too fast to follow under the standard TEM imaging conditions. Although this presents a challenge for traditional structural characterisation of POM molecules, we harness this effect by controlling the conditions around the molecules and tuning the imaging parameters in TEM, which combined with theoretical modelling and image simulation, can shed light on the atomistic mechanisms of the reactions of POMs. This approach, based on the direct space and real time chemical reaction analysis by TEM, adds a new method to the arsenal of single-molecule kinetics techniques.

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Abstract: Electron ptychography is a 4-D STEM phase-contrast imaging technique with applications to light-element and beam-sensitive materials. Although the electron dose (electrons incident per unit area on the sample) is the primary figure of merit for imaging beam-sensitive materials, it is also necessary to consider the contrast transfer properties of the imaging technique. Here, we explore the contrast transfer properties of electron ptychography. The contrast transfer of focused-probe, non-iterative electron ptychography using the single-side-band (SSB) method is demonstrated experimentally. The band-pass nature of the phase-contrast transfer function (PCTF) for SSB ptychography places strict limitations on the probe convergence semi-angles required to resolve specific sample features with high contrast. The PCTF of the extended ptychographic iterative engine (ePIE) is broader than that for SSB ptychography, although when both high and low spatial frequencies are transferred, band-pass filtering is required to remove image artefacts. Normalisation of the transfer function with respect to the noise level shows that the transfer window is increased while avoiding noise amplification. Avoiding algorithms containing deconvolution steps may also increase the dose-efficiency of ptychographic phase reconstructions.

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Abstract: Synchrotron Fe‐K X‐ray absorption spectroscopy and transmission electron microscopy have been used to investigate the mineralogy and Fe‐redox variations in the space‐weathered (SW) rims of asteroidal samples. This study focuses on the FIB lift‐out sections from five Itokawa grains, returned by the Hayabusa spacecraft, including samples RB‐QD04‐0063, RB‐QD04‐0080, RB‐CV‐0011, RB‐CV‐0089, and RB‐CV‐0148. Each of the samples featured partially amorphized SW rims, caused by irradiation damage from implanted low mass solar wind ions, and the impacting of micrometeorites. Using bright‐field and HAADF‐STEM imaging, vesicular blistering and nanophase Fe metal (npFe0) particles were observed within grain rims, and solar flare tracks were observed in the substrate host grain, confirming the presence of SW zones. We use Fe‐K XANES mapping to investigate Fe‐redox changes between the host mineral and the SW zones. All SW zones measured show some increases in the ferric‐ferrous ratio (Fe3+/ΣFe) relative to their respective host grains, likely the result of the implanted solar wind H+ ions reacting with the segregated ferrous Fe in the surface material.

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Abstract: Carbon supported Cu nanoparticles have a remarkable selectivity towards the catalytic dehydrogenation of bioethanol to acetaldehyde, which is an interesting alternative to the preparation from ethylene. In this work, we prepared a series of catalysts comprised of Cu nanoparticles supported on N‐doped ordered mesoporous carbons to investigate the catalytic effect of nitrogen content. Our study shows that N‐doping has a significant effect on the dispersion of Cu nanoparticles and that the highest content of N results in the highest activity. Furthermore, we show that the combined effects of strong metal‐support interactions and nano‐confinement is an effective method to prevent thermal and steam induced sintering. In contrast, we find no evidence that N‐doping activates the substrate or change the rate‐determining step. At 260 °C, the best catalyst results in >99 % selectivity and a site‐time yield of 175 molacetaldehyde/molCu/h. Under these conditions, the catalysts are stable for more than 12 h using an aqueous solution of 10 % ethanol as feed.