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Activity of iron pyrite towards low-temperature ammonia production
© 2016 In this work we report the characteristics of iron pyrite toward the production of ammonia at low temperatures under ultra-high vacuum conditions. We review (with additional unpublished details) our previous systematic study of nitrogen and hydrogen adsorption on single-crystal iron pyrite (FeS 2 ) and summarise our earlier findings regarding the possibility of ammonia synthesis on this material. We also present new results concerning the adsorption of nitrogen and hydrogen on two related materials, namely molybdenum-treated iron pyrite surfaces and iron pyrite nanostructures deposited on a gold single-crystal. On the bare iron pyrite samples, ammonia is produced upon hydrogenation of preadsorbed N species at 230 K, demonstrating that all hydrogenation steps are possible at low pressures and temperatures. Nitrogen adsorbs molecularly on FeS 2 {100} at low temperatures, desorbing at 130 K, but does not adsorb dissociatively even at pressures up to 1 bar. Adsorbed nitrogen species can, however, be obtained through exposure to excited nitrogen species. Hydrogen adsorbs on FeS 2 {100}, but only in the presence of an incandescent Ta filament. Recombinative desorption of H 2 occurs at 225 K and is accompanied by desorption of H 2 S at 260 K. On the molybdenum-treated iron-pyrite, no appreciable N ads species were detected under the experimental conditions studied, and the same is true for iron pyrite nanostructures on Au{111}. We also provide further details of our efficient and reproducible method for preparing well-ordered stoichiometrically pure FeS 2 {100} suitable for surface science studies
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On the Symmetry and Structure of Cubic Semiconductor Surfaces
A systematic stereographic approach to the description of surface symmetry and structure, applied previously to face-centred cubic, body-centred cubic and hexagonal close-packed metals, is here extended to the surfaces of diamond-structure and zincblende-structure semiconductors. A variety of symmetry--structure combinations are categorised, and the chiral properties of certain cases emphasised. A general condition for non-polarity in the surfaces of zincblende materials is also noted
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Spontaneous local symmetry breaking: A conformational study of glycine on Cu{311}
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Understanding the interplay between intrinsic molecular chirality and chirality of the bonding footprint is crucial in exploiting enantioselectivity at surfaces. As such, achiral glycine and chiral alanine are the most obvious candidates if one is to study this interplay on different surfaces. Here, we have investigated the adsorption of glycine on Cu{311} using reflectionâabsorption infrared spectroscopy, low-energy electron diffraction, temperature-programmed desorption, and first-principles density-functional theory. This combination of techniques has allowed us to accurately identify the molecular conformations present under different conditions and discuss the overlayer structure in the context of the possible bonding footprints. We have observed coverage-dependent local symmetry breaking, with three-point bonded glycinate moieties forming an achiral arrangement at low coverages, and chirality developing with the presence of two-point bonded moieties at high coverages. Comparison with previous work on the self-assembly of simple amino acids on Cu{311} and the structurally similar Cu{110} surface has allowed us to rationalize the different conditions necessary for the formation of ordered chiral overlayers.We acknowledge financial support from the Engineering and Physical Sciences Research Council.This is the final version of the manuscript. It first appeared from ACS via http://dx.doi.org/10.1021/acs.jpcc.5b0234
Proline-derived structural phases on Cu{311}
Structural phases formed by adsorption of L-proline onto a Cu{311} surface in ultra-high vacuum were investigated using reflection-absorption infrared spectroscopy, low-energy electron diffraction and scanning tunnelling microscopy. An ordered structural phase formed by self-assembly of L-prolinate with (2,1;1,2) periodicity, and a transition from pure l3 bonding to a mixture of l3 and l2 bonding with increasing exposure at 300 K, were observed. This behaviour has broad parallels with that previously seen with alaninate and glycinate on Cu{311}, but the detailed correlation between structure and bonding, and their evolution during subsequent annealing, are markedly different for prolinate as compared to alaninate and glycinate. At annealing temperatures around 480â490 K, a new structural phase with (5,3;4,6) periodicity emerges. We tentatively attribute this to pyrrole-2-carboxylate, formed by dehydrogenation and aromatization of the pyrrolidine ring of prolinate. The observation of equal areas of the two possible mirror domains associated with the two possible adsorbateâsubstrate bonding enantiomers implies a prochiral intermediate.The Engineering and Physical Sciences Research Council is acknowledged for financial support.This is the final published version. It first appeared at http://link.springer.com/article/10.1007/s11244-015-0400-2
Structure of the large terminase from a hyperthermophilic virus reveals a unique mechanism for oligomerization and ATP hydrolysis
The crystal structure of the large terminase from the Geobacillus stearothermophilus bacteriophage D6E shows a unique relative orientation of the N-terminal adenosine triphosphatase (ATPase) and C-terminal nuclease domains. This monomeric âinitiationâ state with the two domains âlockedâ together is stabilized via a conserved C-terminal arm, which may interact with the portal protein during motor assembly, as predicted for several bacteriophages. Further work supports the formation of an active oligomeric state: (i) AUC data demonstrate the presence of oligomers; (ii) mutational analysis reveals a trans-arginine finger, R158, indispensable for ATP hydrolysis; (iii) the location of this arginine is conserved with the HerA/FtsK ATPase superfamily; (iv) a molecular docking model of the pentamer is compatible with the location of the identified arginine finger. However, this pentameric model is structurally incompatible with the monomeric âinitiationâ state and is supported by the observed increase in kcat of ATP hydrolysis, from 7.8 ± 0.1 minâ1 to 457.7 ± 9.2 minâ1 upon removal of the C-terminal nuclease domain. Taken together, these structural, biophysical and biochemical data suggest a model where transition from the âinitiationâ state into a catalytically competent pentameric state, is accompanied by substantial domain rearrangements, triggered by the removal of the C-terminal arm from the ATPase active site
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Epitaxial growth of few-layer MoS2(0001) on FeS2{100}.
Physical vapour deposition of Mo on an FeS2{100} surface was performed at 170 K. Near-epitaxial growth of MoS2(0001) overlayers of the order of 1 nm thickness was observed when the Mo-covered substrate was subsequently heated to 600 K.The authors thank the EPSRC (grant ref. EP/E039782/1) for
funding.This is the final published version. It first appeared at http://pubs.rsc.org/en/Content/ArticleLanding/2015/CC/c4cc06628f#!divAbstract
Zooâhoused mammals do not avoid giving birth on weekends
There is evidence that zoo visitor presence can influence the behaviour and, in some cases, adrenal response of zoo animals, and can sometimes compromise animal welfare. In some laboratory studies, significantly more primate births have been reported on weekends, when fewer people are working there, compared with weekdays when staffing levels are at their highest. Here, we investigate whether there is evidence of a "weekend effect" on births in zoo animals as a result of visitor numbers. Unlike laboratories, zoos are typically busier with visitors on weekends than on weekdays, although staffing levels remain fairly consistent across days of the week. If zoo animal parturition is sensitive to human presence, then fewer births would be expected on weekends compared with weekdays. We tested this using birth data and visitor numbers on the entrance gate from zoo records across 16 species representing artiodactyls, perissodactyls, carnivores and primates at four British zoos, to see whether there is an association between mean daily birth rates and average visitor numbers. We predict that, if there is a visitor effect, daily births should be lower on weekends than weekdays and should correlate with mean daily visitor numbers. Results showed that births for all 16 species were randomly distributed through the week, and there was no significant decline in births on weekends. We conclude that the âweekend effectâ, if such a thing exists, does not appear to be a feature of zoo births, suggesting that elevated weekend visitor numbers are not sufficiently stressful to trigger delayed parturition
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The crystalline structure of the phenazine overlayer physisorbed on a graphite surface
The monolayer crystal structure of phenazine adsorbed on graphite is determined by a combination of synchrotron X-ray diffraction and DFT calculations. The molecules adopt a rectangular unit cell with lattice parameters a = 13.55 Ă
and b = 10.55 Ă
, which contains 2 molecules. The plane group of the unit cell is p2gg, and each molecule is essentially flat to the plane of the surface, with only a small amount of out-of-plane tilt. Density Functional Theory (DFT) calculations find a minimum energy structure with a unit cell which agrees within 7.5% with that deduced by diffraction. DFT including dispersion force corrections (DFT+D) calculations help to identify the nature of the intermolecular bonding. The overlayer interactions are principally van der Waals, with a smaller contribution from weak C-HâąâąâąN hydrogen bonds. This behaviour is compared with that of 4,4â-bipyridyl.We acknowledge financial support for AB from an EPSRC DTA award from the Department of Chemistry, University of Cambridge; and BP for financial support for CT. We thank Diamond Light Source for access to beamline I11 (EE7761) that contributed to the results presented here. The DFT calculations were performed using the Darwin Supercomputer of the University of Cambridge High Performance Computing Service.This is the accepted manuscript. The final version is available from Taylor & Francis at http://www.tandfonline.com/doi/abs/10.1080/00268976.2013.793844#.VGHd34XziEo
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Increased thermal stability of activated N2 adsorbed on K-promoted Ni{110}
Industrial synthesis of ammonia takes place at high temperatures and pressures via the dissociative adsorption of molecular nitrogen on a transition metal catalyst. In contrast, biological ammonia synthesis occurs under ambient conditions via the hydrogenation of intact molecular nitrogen at the active site of an enzyme. We hypothesise that the latter process may be mimicked within an inorganic system if the intact nitrogen molecule can be polarised, rendering it particularly susceptible to attack by hydrogen. Furthermore, by analogy with the surface chemistry of carbon monoxide at alkali-modified nickel and cobalt surfaces, we consider whether such a polarisation may be achieved by coadsorption with potassium on the same or similar transition metals. Here, we report on reflection absorption infrared spectroscopy results, interpreted with the aid of first-principles density functional calculations, which reveal both similarities and differences between the behaviour of carbon monoxide and nitrogen. Importantly, our calculations suggest that the surface-induced dipole of molecular nitrogen can indeed be enhanced by the coadsorbed alkali metal
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Infrared Spectroscopy of Ammonia on Iron: Adsorption, Synthesis and the Influence of Oxygen
We report on reflection absorption infrared spectroscopy (RAIRS) investigations into the influence of oxygen on the surface chemistry of NH3 on Fe{111}. Pre-adsorption of oxygen is found to strengthen the interaction between ammonia and the surface, albeit at the lowest oxygen coverage examined the effect is only notable when the ammonia
coverage becomes high. At higher oxygen coverage, the same effect is observed even with very low ammonia coverage. In cases where the oxygen overlayer is ordered, the effects are seen quite clearly, but for disordered overlayers the surface heterogeneity makes assignment of absorption features more difficult; nevertheless, comparison with the
ordered examples allows us to identify the same underlying behaviour. When potassium is coadsorbed with oxygen, the effect on ammonia adsorption is threefold, including potassium-dominated and oxygen-dominated features, alongside features that suggest either cancelling or absent influences from the atomic adsorbates. Synthesis of ammonia from nitrogen adatoms in 0.6 mbar H2 shows clear evidence of very similar surface interactions
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