| 1. |
- Dell'Angela, M., et al.
(författare)
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Real-Time Observation of Surface Bond Breaking with an X-ray Laser
- 2013
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 339:6125, s. 1302-1305
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Tidskriftsartikel (refereegranskat)abstract
- We used the Linac Coherent Light Source free-electron x-ray laser to probe the electronic structure of CO molecules as their chemisorption state on Ru(0001) changes upon exciting the substrate by using a femtosecond optical laser pulse. We observed electronic structure changes that are consistent with a weakening of the CO interaction with the substrate but without notable desorption. A large fraction of the molecules (30%) was trapped in a transient precursor state that would precede desorption. We calculated the free energy of the molecule as a function of the desorption reaction coordinate using density functional theory, including van der Waals interactions. Two distinct adsorption wells-chemisorbed and precursor state separated by an entropy barrier-explain the anomalously high prefactors often observed in desorption of molecules from metals.
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| 2. |
- Lilja, J., et al.
(författare)
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Esterification of propanoic acid with ethanol, 1-propanol and butanol over a heterogeneous fiber catalyst
- 2005
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Ingår i: Chemical Engineering Journal. - : Elsevier BV. - 1385-8947 .- 1873-3212. ; 115:02-jan, s. 1-12
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Tidskriftsartikel (refereegranskat)abstract
- Esterification kinetics of propanoic acid with ethanol, 1-propanol and butanol over a fibrous polymer-supported sulphonic acid catalyst (Smopex-101) was studied. Experiments were carried out in a batch reactor operating isothermally at three different temperatures: 60, 70 and 75 degrees C (80 degrees C for butanol) and with different initial molar ratios of propanoic acid and alcohol (1:1, 1:2 and 2:1). The fiber catalyst was active and stable in all the experiments. The experimental results were modeled according to a Langmuir-Hinshelwood model and with an advanced adsorption-based model. The activity coefficients were calculated according to the UNIFAC model. The activation energy of esterification of propanoic acid with ethanol was found to be 52.6 kJ/mol, 49.9 kJ/mol with 1-propanol and 47.3 kJ/mol with butanol. The kinetic model, which includes the adsorption of carboxylic acid and water combined with the activities of the species, explained the experimentally recorded concentrations well.
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| 3. |
- Lindström, B., et al.
(författare)
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Diesel fuel reformer for automotive fuel cell applications
- 2009
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Ingår i: International journal of hydrogen energy. - : Elsevier BV. - 0360-3199 .- 1879-3487. ; 34:8, s. 3367-3381
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Tidskriftsartikel (refereegranskat)abstract
- Fuel economy and emission abatement are issues, which are highly prioritized areas in the automotive industry of today. The debate about climate change has in recent years even more emphasized the importance of these issues and has increased the search for finding sustainable technical solutions. This paper describes an effort to develop an innovative and environmentally-benign hydrogen generation system operating on commercial diesel fuel to avoid running the engine to supply electricity at stand-still. The use of a fuel cell-based auxiliary power unit (APU) has the potential of delivering electricity at high efficiencies independent of the heavy-duty truck engine. During the reformer development phase, spray formation and mixing of reactants proved to be crucial to obtain high reforming efficiencies and low diesel slip. The diesel is being injected through a nozzle creating a spray of fine droplets of a size which can establish rapid evaporation. Air and steam are being pre-heated and injected into the mixture chamber and subsequently mixed with the evaporated diesel fuel. Depending on the operating parameters, a part of the fuel is being oxidized and produces heat. Autothermal reforming was chosen to circumvent the heat transfer problem in catalytic steam reforming. By supplying heat directly to the catalyst surface by an oxidation reaction the heat demand of the strongly endothermic steam reforming reaction can be fulfilled. We employed CFD calculations, which revealed the importance of avoiding large recirculation zones leading to a prolonged residence time of the hydrocarbon molecules and causing auto-ignition and excessive temperatures in the catalyst. Five different reformer generations are being described and discussed in detail in this publication. The first one was based on a fixed bed reactor, while the other four all relied on catalytic monoliths enabling low pressure drops. The early reactor designs all suffered from auto-ignition and instability problems. The latter generations exhibited a considerably more stable temperature profile in the reformer. The conversion of diesel and the reformer efficiencies are significantly higher than the early generation diesel reformers.
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| 4. |
- Mogelhoj, A., et al.
(författare)
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Ab Initio van der Waals Interactions in Simulations of Water Alter Structure from Mainly Tetrahedral to High-Density-Like
- 2011
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-5207 .- 1520-6106. ; 115:48, s. 14149-14160
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Tidskriftsartikel (refereegranskat)abstract
- The structure of liquid water at ambient conditions is studied in ab initio molecular dynamics simulations in the NVE ensemble using van der Waals (vdW) density-functional theory, i.e., using the new exchange-correlation functionals optPBE-vdW and vdW-DF2, where the latter has softer nonlocal correlation terms. Inclusion of the more isotropic vdW interactions counteracts highly directional hydrogen bonds, which are enhanced by standard functionals. This brings about a softening of the microscopic structure of water, as seen from the broadening of angular distribution functions and, in particular, from the much lower and broader first peak in the oxygen-oxygen pair-correlation function (PCF) and loss of structure in the outer hydration shells. Inclusion of vdW interactions is shown to shift the balance of resulting structures from open tetrahedral to more close-packed. The resulting O-O PCF shows some resemblance with experiment for high-density water (Soper, A. K.; Ricci, M.A. Phys. Rev. Lett. 2000, 84, 2881), but not directly with experiment for ambient water. Considering the accuracy of the new functionals for interaction energies, we investigate whether the simulation protocol could cause the deviation. An O-O PCF consisting of a linear combination of 70% from vdW-DF2 and 30% from low-density liquid water, as extrapolated from experiments, reproduces near-quantitatively the experimental O-O PCF for ambient water. This suggests the possibility that the new functionals maybe reliable and that instead larger-scale simulations in the NPT ensemble, where the density is allowed to fluctuate in accordance with proposals for supercooled water, could resolve the apparent discrepancy with the measured PCF.
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| 5. |
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| 6. |
- Xin, H., et al.
(författare)
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Strong Influence of Coadsorbate Interaction on CO Desorption Dynamics on Ru(0001) Probed by Ultrafast X-Ray Spectroscopy and Ab Initio Simulations
- 2015
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Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 114:15
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Tidskriftsartikel (refereegranskat)abstract
- We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distribution and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5 sigma and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.
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| 7. |
- Östrom, Henrik, et al.
(författare)
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Probing the transition state region in catalytic CO oxidation on Ru
- 2015
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 347:6225, s. 978-982
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Tidskriftsartikel (refereegranskat)abstract
- Femtosecond x-ray laser pulses are used to probe the carbon monoxide (CO) oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and oxygen (O) on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the OK-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC-O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.
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| 8. |
- Beye, M., et al.
(författare)
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Selective Ultrafast Probing of Transient Hot Chemisorbed and Precursor States of CO on Ru(0001)
- 2013
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Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 110:18
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Tidskriftsartikel (refereegranskat)abstract
- We have studied the femtosecond dynamics following optical laser excitation of CO adsorbed on a Ru surface by monitoring changes in the occupied and unoccupied electronic structure using ultrafast soft x-ray absorption and emission. We recently reported [M. Dell'Angela et al. Science 339, 1302 (2013)] a phonon-mediated transition into a weakly adsorbed precursor state occurring on a time scale of >2 ps prior to desorption. Here we focus on processes within the first picosecond after laser excitation and show that the metal-adsorbate coordination is initially increased due to hot-electron-driven vibrational excitations. This process is faster than, but occurs in parallel with, the transition into the precursor state. With resonant x-ray emission spectroscopy, we probe each of these states selectively and determine the respective transient populations depending on optical laser fluence. Ab initio molecular dynamics simulations of CO adsorbed on Ru(0001) were performed at 1500 and 3000 K providing insight into the desorption process.
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| 9. |
- Eriksson, Lars, et al.
(författare)
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Modeling of a turbocharged SI engine
- 2002
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Ingår i: Annual Reviews in Control. - 1367-5788 .- 1872-9088. ; 26 I, s. 129-137
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Tidskriftsartikel (refereegranskat)abstract
- Turbocharged SI engines are a major possibility in the current trend of down-sized engines with preserved drivability performance. Considering control and supervision it is favorable to have a mean value model to be used e.g. in observer design. Such models of turbo engines are similar to those of naturally aspirated engines, but there are some special characteristics, e.g. the interconnected gas flows, the intercooler, the difference in relative sizes between the gas volumes (compared to naturally aspirated engines), the turbo, and the waste gate. Here, a model is developed with a strategy to find a model for each engine component (air filter, compressor, after cooler (or intercooler), throttle, engine, turbine, waste gate, and a lumped model for the catalyst and exhaust) as they behave in an engine setting. When investigating agreement with measured data and sensitivity of possible model structures, a number of interesting issues are raised. The experiments and the model validation have been performed on a Saab 2.3 1 production engine.
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| 10. |
- Hansson, Lars-Anders, et al.
(författare)
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Consumption patterns, complexity and enrichment in aquatic food chains
- 1998
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Ingår i: Royal Society of London. Proceedings B. Biological Sciences. - : The Royal Society. - 1471-2954. ; 265:1399, s. 901-906
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Tidskriftsartikel (refereegranskat)abstract
- The interactions between consumers and prey, and their impact on biomass distribution among trophic levels, are central issues in both empirical and theoretical ecology. In a long-term experiment, where all organisms, including the top predator, were allowed to respond to environmental conditions by reproduction, we tested predictions from `prey-dependent' and `ratio-dependent' models. Prey-dependent models made correct predictions only in the presence of strong interactors in simple food chains, but failed to predict patterns in more complex situations. Processes such as omnivory, consumer excretion, and unsuitable prey-size windows (invulnerable prey) increased the complexity and created patterns resembling ratio-dependent consumption. However, whereas the prey-dependent patterns were created by the mechanisms predicted by the model, ratio-dependent patterns were not, suggesting that they may be right for the wrong reason'. We show here that despite the enormous complexity of ecosystems, it is possible to identify and disentangle mechanisms responsible for observed patterns in community structure, as well as in biomass development of organisms ranging in size from bacteria to fish.
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