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Abstract: Synchrotron radiation is emitted from a bending magnet source in a wide ray fan which is collected by the first optical element in a beamline. In order to maximize angular acceptance, and hence flux, it is beneficial to increase the length of this mirror and optical design requirements may necessitate that the optical surface be over 1 m in length. Such mirrors also require cooling as they may be subject to high heat loads from the incident radiation. Two beamlines, B07 and B24, at Diamond Light Source, UK, use 1.4 m long toroidal mirrors which utilize a similar side-clamped cooling manifold design. While this scheme has been successful in providing effective cooling of the mirror, it has also been discovered that it introduces deformation of the radius of curvature which is sufficient to alter the focusing characteristics of the mirror. At both beamlines, the horizontal focus of the beam was found to differ by up to several meter from the design position at the exit slit which resulted in poor flux throughput, reduced energy resolution and other side effects. A pencil beam scan method has been used to diagnose this issue and infer the position of the focus and mirror shape. Through the use of a standalone chiller to alter the temperature of the water within the cooling loop, it has been possible to correct the distortion of the radius and restore the focus to its nominal position.

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Abstract: The co-adsorption of hydrogen with a simple chiral modifier, alanine, on Ni{111} was studied using Density Functional Theory in combination with ambient-pressure X-ray photoelectron spectroscopy and X-ray absorption spectroscopy at temperatures of 300~K and above, which are representative of chiral hydrogenation reactions. Depending on the hydrogen pressure, the surface enables protons to "pop on and off" the modifier molecules, thus significantly altering the adsorption geometry and chemical nature of alanine from anionic tridentate in ultra-high vacuum to predominantly zwitterionic bidentate at hydrogen pressures above 0.1 Torr. This hydrogen-stabilised modifier geometry allows alternative mechanisms for proton transfer and the creation of enatioselective reaction environments.

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Abstract: The hydrogenation of methyl acetoacetate (MAA) over modified Ni catalysts is one of the most important and best studied reactions in heterogeneous enantioselective catalysis. Yet, very little molecular-level information is available on the adsorption complex of the reactant. Here, we report on a combined experimental and theoretical study of MAA adsorption on Ni{111}. XPS shows that the chemisorbed layer is stable up to 250 K; above 250 K, decomposition sets in. In ultra-high-vacuum conditions, multilayers grow below 150 K. DFT modeling predicts a deprotonated enol species with bidentate coordination on the flat Ni{111} surface. The presence of adatoms on the surface leads to stronger MAA adsorption in comparison with the flat surface, whereby the stabilization energy is high enough for MAA to drive the formation of adatom defects at Ni{111}, assuming the adatoms come from steps. Comparison of experimental XPS and NEXAFS data with theoretical modeling, however, identifies the bidentate deprotonated enol on the flat Ni{111} surface as the dominant species at 250 K, indicating that the formation of adatom adsorption complexes is kinetically hindered at low temperatures.

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Abstract: Intrinsically chiral metal surfaces provide enantiospecific reaction environments without the need of co-adsorbed modifiers. Amongst the intrinsically chiral copper surfaces, Cu{531} has the smallest unit cell and the highest density of chiral sites. XPS, NEXAFS and TPD were employed to investigate the adsorption and decomposition behaviour of the two chiral enantiomers of tartaric acid on this surface. The results obtained from XPS and NEXAFS show that at saturation coverage both enantiomers of tartaric acid adsorb in a μ4 configuration through the two carboxylic groups, which are rotated with respect to each other by 90° ± ≈ 15° within the surface plane. At intermediate coverage the R,R enantiomer adopts a similar configuration, but the S,S enantiomer is different and shows a high degree of dissociation. Growth of multilayers is observed at high exposures when the sample is kept at below 370 K. TPD experiments show that multilayers desorb between 390 K and 470 K and decomposition of the chemisorbed layer occurs between 470 K and 600 K. The desorption spectra support a two-step decomposition mechanism with a Odouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashO or HO–HCdouble bond; length as m-dashCH–OH intermediate that leads to production of CO2 and CO. Enantiomeric differences are observed in the desorption features related to the decomposition of the chemisorbed layer.

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Abstract: The intermetallic compound InPd (CsCl type of crystal structure with a broad compositional range) is considered as a candidate catalyst for the steam reforming of methanol. Single crystals of this phase have been grown to study the structure of its three low-index surfaces under ultra-high vacuum conditions, using low energy electron diffraction (LEED), X-ray photoemission spectroscopy (XPS), and scanning tunneling microscopy (STM). During surface preparation, preferential sputtering leads to a depletion of In within the top few layers for all three surfaces. The near-surface regions remain slightly Pd-rich until annealing to ∼580 K. A transition occurs between 580 and 660 K where In segregates towards the surface and the near-surface regions become slightly In-rich above ∼660 K. This transition is accompanied by a sharpening of LEED patterns and formation of flat step-terrace morphology, as observed by STM. Several superstructures have been identified for the different surfaces associated with this process. Annealing to higher temperatures (≥750 K) leads to faceting via thermal etching as shown for the (110) surface, with a bulk In composition close to the In-rich limit of the existence domain of the cubic phase. The Pd-rich InPd(111) is found to be consistent with a Pd-terminated bulk truncation model as shown by dynamical LEED analysis while, after annealing at higher temperature, the In-rich InPd(111) is consistent with an In-terminated bulk truncation, in agreement with density functional theory (DFT) calculations of the relative surface energies. More complex surface structures are observed for the (100) surface. Additionally, individual grains of a polycrystalline sample are characterized by micro-spot XPS and LEED as well as low-energy electron microscopy. Results from both individual grains and “global” measurements are interpreted based on comparison to our single crystals findings, DFT calculations and previous literature