Solid catalysts with ionic liquid layers (SCILLs) show improved performance as compared to ionic liquid (IL)-free catalysts. To realize the beneficial IL-induced modification, the IL layer should be ...stable under reaction conditions but also permeable for gaseous reactants entering through the IL phase. Herein, we applied (polarization modulation-) infrared reflection absorption spectroscopy ((PM-)IRAS) to investigate the CO permeability of model SCILL systems. We investigated three different IL model systems prepared by physical vapor deposition (PVD) in ultrahigh vacuum (UHV) on atomically clean Pt(111), namely, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (C4C1PyrNTf2), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (C2C1ImNTf2), and 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate (C4C1PyrOTf). The adsorption geometries of the anions depend on the surface structure, IL coverage, and precoverage of CO. At room temperature, IL multilayers of randomly oriented species grow on top of strongly adsorbed wetting layers. Upon heating, a partial wetting transition induces the coexistence of an IL wetting monolayer film with three-dimensional droplets. Gas-phase CO does not permeate through IL multilayers, while it penetrates the IL wetting monolayer leading to mixed IL/CO films. The partial dewetting transition and the permeability differ drastically with the temperature and IL. Consequently, the morphology of the IL films could be a factor that determines the catalytic behavior of SCILLs to a significant extent.
Solid catalysts with ionic liquid layers (SCILLs) are heterogeneous catalysts which benefit significantly in terms of selectivity from a thin coating of an ionic liquid (IL). In the present work, we ...study the interaction of CO with a Pd model SCILL consisting of a 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)-imide (C
4
C
1
PyrNTf
2
) film deposited on Pd(111). We investigate the CO permeability and stability of the IL film via pressure modulation experiments by infrared reflection absorption spectroscopy (IRAS) in ultrahigh vacuum (UHV) and at ambient pressure conditions by time-resolved, temperature-programmed, and polarization-modulated (PM) IRAS experiments. In addition, we performed molecular dynamics (MD) simulations to identify adsorption motifs, their abundance, and the influence of CO. We find a strongly bound IL wetting monolayer (ML) and a potentially dewetting multilayer. Molecular reorientation of the IL at the interface and multilayer dewetting allow for the accumulation of CO at the metal/IL interface. Our results confirm that co-adsorption of CO changes the molecular structure of the IL wetting layer which confirms the importance to study model SCILL systems under in situ conditions.
Graphical abstract
The water gas shift reaction (WGSR) is catalyzed by supported ionic liquid phase (SILP) systems containing homogeneous Ru complexes dissolved in ionic liquids (ILs). These systems work at very low ...temperatures, that is, between 120 and 160 °C, as compared to >200 °C in the conventional process. To improve the performance of this ultra-low-temperature catalysis, we investigated the influence of various additives on the catalytic activity of these SILP systems. In particular, the application of methylene blue (MB) as an additive doubled the activity. Infrared spectroscopy measurements combined with density functional theory (DFT) calculations excluded a coordinative interaction of MB with the Ru complex. In contrast, state-of-the-art theoretical calculations elucidated the catalytic effect of the additives by non-covalent interactions. In particular, the additives can significantly lower the barrier of the rate-determining step of the reaction mechanism via formation of hydrogen bonds. The theoretical predictions, thereby, showed excellent agreement with the increase of experimental activity upon variation of the hydrogen bonding moieties in the additives investigated.
To determine computed tomographic (CT) features of early type II endoleaks associated with aneurysm sac enlargement after endovascular aortic aneurysm repair (EVAR) of abdominal aortic aneurysm.
...Institutional review board approval was not required for this retrospective study. The authors reviewed imaging and clinical data from 56 patients (seven women, 49 men; mean age ± standard deviation, 71 years ± 7.9; age range, 52-85 years) with early type II endoleak who had undergone EVAR between December 2002 and December 2011 and who had been followed up with imaging and clinical evaluation for at least 6 months. The number and diameter of all feeding and/or draining arteries were measured, and endoleaks were classified according to their sources into simple inferior mesenteric artery (IMA), simple lumbar artery (LA), complex LA, and complex IMA-LA type II endoleaks. Volume and attenuation of the nidus were measured. Aneurysm enlargement was defined as an increase in the aneurysm volume of more than 5% during follow-up. Simple and multivariate logistic regression analyses were performed to identify independent clinical and imaging variables associated with aneurysm enlargement.
Twenty-three of the 56 patients (41%) showed aneurysm sac enlargement during follow-up (mean follow-up, 3.0 years ± 2.0). With the multivariate model, the variables that showed the strongest indicators for aneurysm sac enlargement were complex IMA-LA type II endoleak (odds ratio OR = 10.29, P = .004) and the diameter of the largest feeding and/or draining artery (OR = 4.55, P = .013). Patients without complex IMA-LA type II endoleak in whom the largest feeding and/or draining artery was larger than 3.8 mm and patients with a complex IMA-LA type II endoleak in whom the largest feeding and/or draining artery was larger than 2.2 mm were at high risk for aneurysm sac enlargement.
The strongest indicators for aneurysm sac enlargement are complex IMA-LA type II endoleak and the diameter of the largest feeding and/or draining artery.
Interference experiments with electrons in a vacuum can illuminate both the quantum and the nanoscale nature of the underlying physics. An interference experiment requires two coherent waves, which ...can be generated by splitting a single coherent wave using a double slit. If the slit-edge separation is larger than the coherence width at the slit, no interference appears. Here we employed variations in surface barrier at the apex of a tungsten nano-tip as slits and achieved an optically controlled double slit, where the separation and opening-and-closing of the two slits can be controlled by respectively adjusting the intensity and polarization of ultrashort laser pulses. Using this technique, we have demonstrated interference between two electron waves emitted from the tip apex, where interference has never been observed prior to this technique because of the large slit-edge separation. Our findings pave the way towards simple time-resolved electron holography on e.g. molecular adsorbates employing just a nano-tip and a screen.
The h-BN nanomesh on Rh(111) is used as eggbox-like template for the formation of arrays of Pt nanoclusters with a narrow size distribution. Nanoclusters with sizes from 1 up to 50 atoms are prepared ...simultaneously in a wedge-like structure by depositing a coverage gradient on the h-BN nanomesh, and thus can be investigated under identical conditions. We studied the preparation and properties of these Pt nanoclusters of different size
in situ
by high-resolution X-ray photoelectron spectroscopy and scanning tunneling microscopy. For a Pt coverage of 0.1 ML, all pores of the h-BN nanomesh are filled with nanoclusters with a remarkably uniform cluster size of 12 Pt atoms per pore, and high stability up to 400 K. Above 0.2 ML Pt, the clusters are less stable. The coverage dependent analysis shows that for Pt coverages below 0.1 ML, the number of nanoclusters is smaller - and the number of empty pores higher - than expected for a simple hit and stick mechanism. We assign this behavior to an initially higher mobility of the Pt atoms in a hot precursor state.
We investigated growth and temperature stability of Pt nanoclusters from 1 to 50 atoms on h-BN/Rh(111) using high-resolution XPS and STM.
Speaker age is a speaker characteristic which is always present in speech. Previous studies have found numerous acoustic features which correlate with speaker age. However, few attempts have been ...made to establish their relative importance. This study automatically extracted 161 acoustic features from six words produced by 527 speakers of both genders, and used normalised means to directly compare the features. Segment duration and sound pressure level (SPL) range were identified as the most important acoustic correlates of speaker age.
This work investigates the suppression of individual harmonics, simultaneously affecting specific even and odd orders in the high-harmonic spectra generated by strongly tailored, two-colour, ...multi-cycle laser pulses in neon. The resulting spectra are systematically studied as a function of the electric-field shape in a symmetry-broken (\(\omega\)-\(2\omega\)) and symmetry-preserved (\(\omega\)-\(3\omega\)) configuration. The peak suppression is reproduced by macroscopic strong-field approximation calculations and is found to be unique to symmetry-broken fields (\(\omega\)-\(2\omega\)). Additionally, semi-classical calculations further corroborate the observation and reveal their underlying mechanism, where a nontrivial spectral interference between subsequent asymmetric half-cycles is found to be responsible for the suppression.
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