Structural and spectroscopic characterisation of C4 oxygenates relevant to structure/activity relationships of the hydrogenation of α,β-unsaturated carbonyls

In the present work, we have investigated the conformational isomerism and calculated the vibrational spectra of the C4 oxygenates: 3-butyne-2-one, 3-butene-2-one, 2-butanone and 2-butanol using density functional theory. The calculations are validated by comparison to structural data where available and new, experimental inelastic neutron scattering and infrared spectra of the compounds. We find that for 3-butene-2-one and 2-butanol the spectra show clear evidence for the presence of conformational isomerism and this is supported by the calculations. Complete vibrational assignments for all four molecules are provided and this provides the essential information needed to generate structure/activity relationships for the sequential catalytic hydrogenation of 3-butyne-2-one to 2-butanol

C II abundances in early-type stars: solution to a notorious non-LTE problem

We address a long-standing discrepancy between non-LTE analyses of the prominent C II 4267 and 6578/82 A multiplets in early-type stars. A comprehensive non-LTE model atom of C II is constructed based on critically selected atomic data. This model atom is used for an abundance study of six apparently slow-rotating main-sequence and giant early B-type stars. High-resolution and high-S/N spectra allow us to derive highly consistent abundances not only from the classical features but also from up to 18 further C II lines in the visual - including two so far unreported emission features equally well reproduced in non-LTE. These results require the stellar atmospheric parameters to be determined with care. A homogeneous (slightly) sub-solar present-day carbon abundance from young stars in the solar vicinity (in associations and in the field) of log C/H +12= 8.29+/-0.03 is indicated.Comment: 8 pages, 5 figure

Hydrogen partitioning as a function of time-on-stream for an unpromoted iron-based Fischer-Tropsch synthesis catalyst applied to CO hydrogenation

Sasol Ltd., the EPSRC (award reference EP/P505534/1), and the University of Glasgow are thanked for the provision of a postgraduate studentship (ALD). The STFC Rutherford Appleton Laboratory is thanked for access to neutron beam facilities. The Royal Society is thanked for the provision of an Industry Fellowship (PBW).Inelastic neutron scattering (INS) is employed to examine the evolution of a promoter-free iron-based Fischer-Tropsch synthesis catalyst (∼10 g catalyst charge) that is exposed to ambient pressure CO hydrogenation at 623 K for up to 10 days time-on-stream (T-o-S). The longer reaction time is selected to better understand how the formation of a previously described hydrocarbonaceous overlayer corresponds to the catalyst conditioning process. Although the onset of pseudo steady-state reactor performance is observed at approximately 9 h T-o-S, INS establishes that the intensity of the C-H stretching mode of the sp3-hybridized component of the hydrocarbonaceous overlayer saturates at about 24 h T-o-S, while the corresponding intensity of the C-H stretching mode of the sp2-hybridized component requires 100-200 h T-o-S to achieve saturation. This novel series of measurements reveal different aspects of the complex catalyst evolutionary process to be indirectly connected with catalytic turnover.Publisher PDFPeer reviewe

A census of massive stars in NGC 346. Stellar parameters and rotational velocities

Spectroscopy for 247 stars towards the young cluster NGC 346 in the Small Magellanic Cloud has been combined with that for 116 targets from the VLT-FLAMES Survey of Massive Stars. Spectral classification yields a sample of 47 O-type and 287 B-type spectra, while radial-velocity variations and/or spectral multiplicity have been used to identify 45 candidate single-lined systems, 17 double-lined systems, and one triple-lined system. Atmospheric parameters (T$_eff$ and log$g$) and projected rotational velocities ($v_e$sin$i$) have been estimated using TLUSTY model atmospheres; independent estimates of $v_e$sin$i$ were also obtained using a Fourier Transform method. Luminosities have been inferred from stellar apparent magnitudes and used in conjunction with the T$_eff$ and $v_e$sin$i$ estimates to constrain stellar masses and ages using the BONNSAI package. We find that targets towards the inner region of NGC 346 have higher median masses and projected rotational velocities, together with smaller median ages than the rest of the sample. There appears to be a population of very young targets with ages of less than 2 Myr, which have presumably all formed within the cluster. The more massive targets are found to have lower $v_e$sin$i$ consistent with previous studies. No significant evidence is found for differences with metallicity in the stellar rotational velocities of early-type stars, although the targets in the SMC may rotate faster than those in young Galactic clusters. The rotational velocity distribution for single non-supergiant B-type stars is inferred and implies that a significant number have low rotational velocity ($\simeq$10\% with $v_e$<40 km/s), together with a peak in the probability distribution at $v_e \simeq$300 km/s. Larger projected rotational velocity estimates have been found for our Be-type sample and imply that most have rotational velocities between 200-450 km/s.Comment: Accepted by A&

Structure/activity relationships applied to the hydrogenation of α,β-unsaturated carbonyls: The hydrogenation of 3-butyne-2-one over alumina-supported palladium catalysts

The gas phase hydrogenation of 3-butyne-2-one, an alkynic ketone, over two alumina-supported palladium catalysts is investigated using infrared spectroscopy in a batch reactor at 373 K. The mean particle size of the palladium crystallites of the two catalysts are comparable (2.4 ± 0.1 nm). One catalyst (Pd(NO3)2/Al2O3) is prepared from a palladium(II) nitrate precursor, whereas the other catalyst (PdCl2/Al2O3) is prepared using palladium(II) chloride as the Pd precursor compound. A three-stage sequential process is observed with the Pd(NO3)2/Al2O3 catalyst facilitating complete reduction all the way through to 2-butanol. However, hydrogenation stops at 2-butanone with the PdCl2/Al2O3 catalyst. The inability of the PdCl2/Al2O3 catalyst to reduce 2-butanone is attributed to the inaccessibility of edge sites on this catalyst, which are blocked by chlorine retention originating from the catalyst’s preparative process. The reaction profiles observed for the hydrogenation of this alkynic ketone are consistent with the site-selective chemistry recently reported for the hydrogenation of crotonaldehyde, an alkenic aldehyde, over the same two catalysts. Thus, it is suggested that a previously postulated structure/activity relationship may be generic for the hydrogenation of α,β-unsaturated carbonyl compounds over supported Pd catalysts

The application of inelastic neutron scattering to investigate the interaction of methyl propanoate with silica

A modern industrial route for the manufacture of methyl methacrylate involves the reaction of methyl propanoate and formaldehyde over a silica-supported Cs catalyst. Although the process has been successfully commercialised, little is known about the surface interactions responsible for the forward chemistry. This work concentrates upon the interaction of methyl propanoate over a representative silica. A combination of infrared spectroscopy, inelastic neutron scattering, DFT calculations, X-ray diffraction and temperature-programmed desorption is used to deduce how the ester interacts with the silica surface