Paul B. Webb

Insight into the detailed bulk and surface structure of γ-Al₂O₃ is provided by a NMR crystallographic approach, exploiting isotopic enrichment, multinuclear experimental measurements and periodic calculations.

A free-standing and compact reaction cell for combined in situ/operando x-ray spectroscopy, scattering, and imaging measurements at high pressures and high temperatures is described. The cell permits measurements under realistic operating conditions (up to 50 bar and 1000 °C), under static and flow conditions (up to 100 ml/min), over a wide range of hard x-ray energies, variable detection modes (transmission, fluorescence, and scattering), and at all angles of rotation. An operando XAS, x-ray fluorescence, x-ray computed tomography, and x-ray diffraction computed tomography case study on the reduction of a heterogeneous catalyst is presented to illustrate the performance of the reaction cell.

The beamline optics and endstations at branch B of the Versatile Soft X-ray (VerSoX) beamline B07 at Diamond Light Source are described. B07-B provides medium-flux X-rays in the range 45–2200 eV from a bending magnet source, giving access to local electronic structure for atoms of all elements from Li to Y. It has an endstation for high-throughput X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine-structure (NEXAFS) measurements under ultrahigh-vacuum (UHV) conditions. B07-B has a second endstation dedicated to NEXAFS at pressures from UHV to ambient pressure (1 atm). The combination of these endstations permits studies of a wide range of interfaces and materials. The beamline and endstation designs are discussed in detail, as well as their performance and the commissioning process.

In fish otoliths, CaCO3 normally precipitates as aragonite, and more rarely as vaterite or calcite. A higher incidence of vaterite deposition in otoliths from aquaculture-reared fish has been reported and it is thought that high growth rates under farming conditions might promote its deposition. To test this hypothesis, otoliths from growth hormone (GH) transgenic coho salmon and non-transgenic fish of matching size were compared. Once morphometric parameters were normalized by animal length, we found that transgenic fish otoliths were smaller (−24%, −19%, −20% and −30% for length, width, perimeter and area, respectively; P<0.001) and rounder (−12%, +13.5%, +15% and −15.5% in circularity, form factor, roundness and ellipticity; P<0.001) than otoliths from non-transgenic fish of matching size. Interestingly, transgenic fish had smaller eyes (−30% eye diameter) and showed a strong correlation between eye and otolith size. We also found that the percentage of otoliths showing vaterite deposition was significantly smaller in transgenic fish (21–28%) than in non-transgenic fish (69%; P<0.001). Likewise, the area affected by vaterite deposition within individual otoliths was reduced in transgenic fish (21–26%) compared with non-transgenic fish (42.5%; P<0.001). Our results suggest that high growth rates per se are not sufficient to cause vaterite deposition in all cases, and that GH overexpression might have a protective role against vaterite deposition, a hypothesis that needs further investigation.

A dual sodium and sulfur promoted haematite, representative of a candidate Fischer-Tropsch to olefins (FTO) catalyst, is prepared and contrasted with the performance of an unpromoted hematite sample in the ambient pressure CO hydrogenation reaction at 623 K as a function of time-on-stream (0–24 h). In-situ post-reaction temperature-programmed oxidation measurements show the carbon evolutionary phase of the catalyst conditioning process to be retarded for the FTO catalyst. Ex-situ inelastic neutron scattering measurements show the promoters perturb the formation of a previously described hydrocarbonaceous overlayer. Specifically, whilst the sp³ hybridised C–H modes of the hydrocarbonaceous overlayer are almost unaffected by the additives, the formation of the overlayer’s sp² hybridised C–H modes are noticeably impeded. The results are discussed in terms of the Na/S promoters disturbing the formation of an ordered hydrocarbonaceous overlayer that is thought to constrain the supply of adsorbed hydrogen atoms, which favours the formation of unsaturated hydrocarbons associated with the FTO process.

Iron-based Fischer–Tropsch synthesis (FTS) catalysts evolve in situ on exposure to synthesis gas (CO & H₂) forming a mixture of iron oxides, iron carbides and carbonaceous deposits. Recently, the application of inelastic neutron scattering has shown the progressive formation of a hydrocarbonaceous overlayer during this catalyst conditioning period. The evolving nature of the catalyst alters the proportion of phases present within the catalyst, which may influence the transport of hydrogen within the reaction system. Preliminary quasi-elastic neutron scattering (QENS) measurements are used to investigate hydrogen diffusion within an un-promoted iron FTS catalyst that has experienced varying levels of time-on-stream (0, 12 and 24 h) of ambient pressure CO hydrogenation at 623 K. Measurements on the catalyst samples in the absence of hydrogen show the unreacted sample (t = 0 h) to exhibit little increase in motion over the temperature range studied, whereas the t = 12 and 24 h samples exhibit a pronounced change in motion with temperature. The contrast is attributed to the presence of the afore-mentioned hydrocarbonaceous overlayer. Measurements on the samples in the presence of liquid hydrogen show hydrogen diffusional characteristics to be modified as a function of the catalyst conditioning process but, due to the complexity of the evolving catalyst matrix, the hydrogen motion cannot be attributed to a particular phase or component of the catalyst. Problems in the use of hydrogen as a probe molecule in this instance are briefly considered. Coincident neutron diffraction studies undertaken alongside the QENS measurements confirm the transition from hematite pre-catalyst to that of Hägg carbide during the course of extended times-on-stream.