| 1. |
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| 2. |
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| 3. |
- Beal, Jacob, et al.
(författare)
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Robust estimation of bacterial cell count from optical density
- 2020
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Ingår i: Communications Biology. - : Springer Science and Business Media LLC. - 2399-3642. ; 3:1
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Tidskriftsartikel (refereegranskat)abstract
- Optical density (OD) is widely used to estimate the density of cells in liquid culture, but cannot be compared between instruments without a standardized calibration protocol and is challenging to relate to actual cell count. We address this with an interlaboratory study comparing three simple, low-cost, and highly accessible OD calibration protocols across 244 laboratories, applied to eight strains of constitutive GFP-expressing E. coli. Based on our results, we recommend calibrating OD to estimated cell count using serial dilution of silica microspheres, which produces highly precise calibration (95.5% of residuals <1.2-fold), is easily assessed for quality control, also assesses instrument effective linear range, and can be combined with fluorescence calibration to obtain units of Molecules of Equivalent Fluorescein (MEFL) per cell, allowing direct comparison and data fusion with flow cytometry measurements: in our study, fluorescence per cell measurements showed only a 1.07-fold mean difference between plate reader and flow cytometry data.
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| 4. |
- Sampson, Joshua N., et al.
(författare)
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Analysis of Heritability and Shared Heritability Based on Genome-Wide Association Studies for 13 Cancer Types
- 2015
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Ingår i: Journal of the National Cancer Institute. - : Oxford University Press (OUP). - 0027-8874 .- 1460-2105. ; 107:12
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Tidskriftsartikel (refereegranskat)abstract
- Background: Studies of related individuals have consistently demonstrated notable familial aggregation of cancer. We aim to estimate the heritability and genetic correlation attributable to the additive effects of common single-nucleotide polymorphisms (SNPs) for cancer at 13 anatomical sites. Methods: Between 2007 and 2014, the US National Cancer Institute has generated data from genome-wide association studies (GWAS) for 49 492 cancer case patients and 34 131 control patients. We apply novel mixed model methodology (GCTA) to this GWAS data to estimate the heritability of individual cancers, as well as the proportion of heritability attributable to cigarette smoking in smoking-related cancers, and the genetic correlation between pairs of cancers. Results: GWAS heritability was statistically significant at nearly all sites, with the estimates of array-based heritability, h(l)(2), on the liability threshold (LT) scale ranging from 0.05 to 0.38. Estimating the combined heritability of multiple smoking characteristics, we calculate that at least 24% (95% confidence interval [CI] = 14% to 37%) and 7% (95% CI = 4% to 11%) of the heritability for lung and bladder cancer, respectively, can be attributed to genetic determinants of smoking. Most pairs of cancers studied did not show evidence of strong genetic correlation. We found only four pairs of cancers with marginally statistically significant correlations, specifically kidney and testes (rho = 0.73, SE = 0.28), diffuse large B-cell lymphoma (DLBCL) and pediatric osteosarcoma (rho = 0.53, SE = 0.21), DLBCL and chronic lymphocytic leukemia (CLL) (rho = 0.51, SE = 0.18), and bladder and lung (rho = 0.35, SE = 0.14). Correlation analysis also indicates that the genetic architecture of lung cancer differs between a smoking population of European ancestry and a nonsmoking Asian population, allowing for the possibility that the genetic etiology for the same disease can vary by population and environmental exposures. Conclusion: Our results provide important insights into the genetic architecture of cancers and suggest new avenues for investigation.
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| 5. |
- Weinstein, John N., et al.
(författare)
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The cancer genome atlas pan-cancer analysis project
- 2013
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Ingår i: Nature Genetics. - : Springer Science and Business Media LLC. - 1061-4036 .- 1546-1718. ; 45:10, s. 1113-1120
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Forskningsöversikt (refereegranskat)abstract
- The Cancer Genome Atlas (TCGA) Research Network has profiled and analyzed large numbers of human tumors to discover molecular aberrations at the DNA, RNA, protein and epigenetic levels. The resulting rich data provide a major opportunity to develop an integrated picture of commonalities, differences and emergent themes across tumor lineages. The Pan-Cancer initiative compares the first 12 tumor types profiled by TCGA. Analysis of the molecular aberrations and their functional roles across tumor types will teach us how to extend therapies effective in one cancer type to others with a similar genomic profile. © 2013 Nature America, Inc. All rights reserved.
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| 6. |
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| 7. |
- Desjardins, Kewin, et al.
(författare)
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Characterization of a back-illuminated CMOS camera for soft x-ray coherent scattering
- 2019
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Ingår i: Proceedings of the 13th International Conference on Synchrotron Radiation Instrumentation, SRI 2018. - : Author(s). - 9780735417823 ; 2054
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Konferensbidrag (refereegranskat)abstract
- A commercial scientific camera has been adapted and characterized at the SOLEIL Synchrotron with the aim to improve the acquisition capabilities on the soft X-ray coherent scattering experimental station at SEXTANTS beamline. This device is equipped by the last generation of back side illuminated scientific CMOS (BSI-sCMOS) of 2048 by 2048 pixels of 11 μm2 able to acquire low noise images with a frame rate up to 48 Hz. The camera's performance measurements have been done and shows a good level of readout noise, a large full-well capacity, a medium dark current and a good homogeneity, respectively, 1.6 e- rms (in High Gain mode), 80 000 e- (in Low Gain mode),<5 e-/pixel/s and ∼ 1%. The quantum efficiency (QE) measurement has been performed at the soft x-ray branch of the METROLOGIE beamline and gives a relatively good agreement with the expected theoretical values. Finally, the demonstration of the camera's efficiency and of the gain in useful time measurement related to the high frame rate have been performed with a series of Airy patterns images compared with an image recorded using the standard BSI-CDD already in operation at the SEXTANTS beamline.
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| 8. |
- Griesmayer, E., et al.
(författare)
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Applications of single-crystal CVD diamond XBPM detectors with nanometre x-ray beams
- 2019
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Ingår i: Proceedings of the 13th International Conference on Synchrotron Radiation Instrumentation, SRI 2018. - : Author(s). - 9780735417823 ; 2054
-
Konferensbidrag (refereegranskat)abstract
- Measurements with a Diamond XBPM were carried out at the MAX IV Laboratory, Lund, Sweden, at the NanoMAX beam line. This was the first investigation of a Diamond XBPM detector with nanometre beams. The effect of diffusion, as well as the position resolution at the smallest available beam sizes were studied.
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| 9. |
- Lin, Chia-Yeh, et al.
(författare)
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H2B Mono-ubiquitylation Facilitates Fork Stalling and Recovery during Replication Stress by Coordinating Rad53 Activation and Chromatin Assembly
- 2014
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Ingår i: PLOS Genetics. - : Public library science. - 1553-7390 .- 1553-7404. ; 10:10, s. e1004667-
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Tidskriftsartikel (refereegranskat)abstract
- The influence of mono-ubiquitylation of histone H2B (H2Bub) on transcription via nucleosome reassembly has been widely documented. Recently, it has also been shown that H2Bub promotes recovery from replication stress; however, the underling molecular mechanism remains unclear. Here, we show that H2B ubiquitylation coordinates activation of the intra-S replication checkpoint and chromatin re-assembly, in order to limit fork progression and DNA damage in the presence of replication stress. In particular, we show that the absence of H2Bub affects replication dynamics (enhanced fork progression and reduced origin firing), leading to γH2A accumulation and increased hydroxyurea sensitivity. Further genetic analysis indicates a role for H2Bub in transducing Rad53 phosphorylation. Concomitantly, we found that a change in replication dynamics is not due to a change in dNTP level, but is mediated by reduced Rad53 activation and destabilization of the RecQ helicase Sgs1 at the fork. Furthermore, we demonstrate that H2Bub facilitates the dissociation of the histone chaperone Asf1 from Rad53, and nucleosome reassembly behind the fork is compromised in cells lacking H2Bub. Taken together, these results indicate that the regulation of H2B ubiquitylation is a key event in the maintenance of genome stability, through coordination of intra-S checkpoint activation, chromatin assembly and replication fork progression.
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| 10. |
- Marcouille, O., et al.
(författare)
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Production of high energy photons with in vacuum wigglers : From SOLEIL wiggler to MAXIV wiggler
- 2019
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Ingår i: Proceedings of the 13th International Conference on Synchrotron Radiation Instrumentation, SRI 2018. - : Author(s). - 9780735417823 ; 2054
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Konferensbidrag (refereegranskat)abstract
- Small gap wigglers become more and more attractive to produce high photon fluxes in the hard X-ray photon range. They use magnet blocks of high magnetization which resists much better to heating (baking, synchrotron radiation) than in the past, produce high magnetic field with numerous periods and are very compact. They also are a very good alternative to superconducting technology which requires special infrastructure, heavy maintenance and is not running cost free. SOLEIL, operating presently at 2.75 GeV has designed and built an in-vacuum wiggler of 38 periods of 50 mm producing 2.1 T at a minimum gap of 5.5 mm to delivered photon beam between 20 keV and 50 keV. Already in operation, further improvements are presently in progress to push photons towards higher energy, in particular thanks to the operation at lower gap (4.5 mm). MAX IV and SOLEIL, in the frame of collaboration, ave built an upgraded version of the existing SOLEIL wiggler with the target to extend the spectral range at high energy (above 50 keV) but also at low energy (4 keV) with the same insertion device. The design of the existing magnetic system has been modified to reach 2.4 T at a minimum gap of 4.2 mm and includes taper operation to avoid undulator structure in the radiated spectrum at low energy.
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| 11. |
- Ogasawara, Hirohito, et al.
(författare)
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X-ray free electron laser studies of electron and phonon dynamics of graphene adsorbed on copper
- 2023
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Ingår i: Physical Review Materials. - 2475-9953. ; 7:2
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Tidskriftsartikel (refereegranskat)abstract
- We report optical pumping and x-ray absorption spectroscopy experiments at the Pohang Accelerator Laboratory free electron laser that probes the electron dynamics of a graphene monolayer adsorbed on copper in the femtosecond regime. By analyzing the results with ab initio theory we infer that the excitation of graphene is dominated by indirect excitation from hot electron-hole pairs created in the copper by the optical laser pulse. However, once the excitation is created in graphene, its decay follows a similar path as in many previous studies of graphene adsorbed on semiconductors, i.e., rapid excitation of strongly coupled optical phonons and eventual thermalization. It is likely that the lifetime of the hot electron-hole pairs in copper governs the lifetime of the electronic excitation of the graphene.
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| 12. |
- Plivelic, Tomás S., et al.
(författare)
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X-ray tracing, design and construction of an optimized optics scheme for CoSAXS, the small angle x-ray scattering beamline at MAX IV laboratory
- 2019
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Ingår i: Proceedings of the 13th International Conference on Synchrotron Radiation Instrumentation, SRI 2018. - : Author(s). - 9780735417823 ; 2054
-
Konferensbidrag (refereegranskat)abstract
- A novel optical design for a flexible SAXS beamline at a modern synchrotron has been implemented for the CoSAXS beamline at the 3GeV ring at the MAX TV Laboratory. The performance of the beamline has been simulated through combined ray tracing and wave propagation with the code xrt taking into account the low emittance and highly coherent beam of MAX TV and the short inter-optics distances of the beamline. The total photon flux is estimated to be 1012-1013 ph/s with the coherent flux portion up to 10 % at 7.1 keV. The inhomogeneities in the X-ray beam arising from use of real (non-idealised) mirror surfaces are also modelled using the measured slope profiles of the mirrors. Strategies to mitigate these inhomogeneities are discussed. The optical components for CoSAXS have been constructed and beamline commissioning will start in 2019.
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| 13. |
- Amann, Peter, et al.
(författare)
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A dedicated photoelectron spectroscopy instrument for studies of catalytic reactions at pressures exceeding 1 bar
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- Here, we present a new high-pressure x-ray photoelectron spectroscopy system dedicated to probing catalytic reactions under realistic conditions at pressures exceeding 1 bar. The instrument builds around the concept of a “virtual cell” in which a gasflow is directed onto the sample surface creating a local high pressure on top of the sample. This allows the instrument to maintain a low pressure of a few mbars in the main chamber, while simultaneously keeping a local pressure of around 1 bar. Synchrotron radiation based grazing incidence photoemission within ± 5° is used to enhance the surface sensitivity in the experiment. The aperture, separating the high-pressure region from the differential pumping of the electron spectrometer, consists of multiple, evenly spaced, mm sized holes matching the footprint of the x-ray beam on the sample surface. As the photo-emitted electrons are subject to strong scattering in the gas phase and the resulting signal is therefore highly dependent on the sample to aperture distance, the latter is controlled with high precision using a fully integrated manipulator that allows for sample movement with step sizes of 10 nm between 0 and –5 mm with very low vibrational amplitude. The instrumental features allows acquisition of metallic bulk spectra at He pressures up to 2.5 bar and also allows for following C1s spectra under realistic gas mixtures of CO + H2with various temperatures up to 500°C. This capability opens for studies of catalytic reactions in operandi.
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| 14. |
- Amann, Peter, et al.
(författare)
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A high-pressure x-ray photoelectron spectroscopy instrument for studies of industrially relevant catalytic reactions at pressures of several bars
- 2019
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Ingår i: Review of Scientific Instruments. - : American Institute of Physics (AIP). - 0034-6748 .- 1089-7623. ; 90:10
-
Tidskriftsartikel (refereegranskat)abstract
- We present a new high-pressure x-ray photoelectron spectroscopy system dedicated to probing catalytic reactions under realistic conditions at pressures of multiple bars. The instrument builds around the novel concept of a "virtual cell" in which a gas flow onto the sample surface creates a localized high-pressure pillow. This allows the instrument to be operated with a low pressure of a few millibar in the main chamber, while simultaneously a local pressure exceeding 1 bar can be supplied at the sample surface. Synchrotron based hard x-ray excitation is used to increase the electron mean free path in the gas region between sample and analyzer while grazing incidence <5 degrees close to total external refection conditions enhances surface sensitivity. The aperture separating the high-pressure region from the differential pumping of the electron spectrometer consists of multiple, evenly spaced, micrometer sized holes matching the footprint of the x-ray beam on the sample. The resulting signal is highly dependent on the sample-to-aperture distance because photoemitted electrons are subject to strong scattering in the gas phase. Therefore, high precision control of the sample-to-aperture distance is crucial. A fully integrated manipulator allows for sample movement with step sizes of 10 nm between 0 and -5 mm with very low vibrational amplitude and also for sample heating up to 500 degrees C under reaction conditions. We demonstrate the performance of this novel instrument with bulk 2p spectra of a copper single crystal at He pressures of up to 2.5 bars and C1s spectra measured in gas mixtures of CO + H-2 at pressures of up to 790 mbar. The capability to detect emitted photoelectrons at several bars opens the prospect for studies of catalytic reactions under industrially relevant operando conditions.
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| 15. |
- Amann, Peter, et al.
(författare)
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The state of zinc in methanol synthesis over a Zn/ZnO/Cu(211) model catalyst
- 2022
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 376:6593, s. 603-608
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Tidskriftsartikel (refereegranskat)abstract
- The active chemical state of zinc (Zn) in a zinc-copper (Zn-Cu) catalyst during carbon dioxide/carbon monoxide (CO2/CO) hydrogenation has been debated to be Zn oxide (ZnO) nanoparticles, metallic Zn, or a Zn-Cu surface alloy. We used x-ray photoelectron spectroscopy at 180 to 500 millibar to probe the nature of Zn and reaction intermediates during CO2/CO hydrogenation over Zn/ZnO/Cu(211), where the temperature is sufficiently high for the reaction to rapidly turn over, thus creating an almost adsorbate-free surface. Tuning of the grazing incidence angle makes it possible to achieve either surface or bulk sensitivity. Hydrogenation of CO2 gives preference to ZnO in the form of clusters or nanoparticles, whereas in pure CO a surface Zn-Cu alloy becomes more prominent. The results reveal a specific role of CO in the formation of the Zn-Cu surface alloy as an active phase that facilitates efficient CO2 methanol synthesis.
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| 16. |
- Degerman, David, 1989-, et al.
(författare)
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Operando Observation of Oxygenated Intermediates during CO Hydrogenation on Rh Single Crystals
- 2022
-
Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 144:16, s. 7038-7042
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Tidskriftsartikel (refereegranskat)abstract
- The CO hydrogenation reaction over the Rh(111) and (211) surfaces has been investigated operando by X-ray photoelectron spectroscopy at a pressure of 150 mbar. Observations of the resting state of the catalyst give mechanistic insight into the selectivity of Rh for generating ethanol from CO hydrogenation. This study shows that the Rh(111) surface does not dissociate all CO molecules before hydrogenation of the O and C atoms, which allows methoxy and other both oxygenated and hydrogenated species to be visible in the photoelectron spectra.
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| 17. |
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| 18. |
- Degerman, David, 1989-, et al.
(författare)
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Surface adsorbates during CO2 Hydrogenation on Rh(111) probed in-situ by x-ray photoelectron spectroscopy at 150 mbar
-
Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- The catalytic CO2 hydrogenation reaction was examined in situ by High Pressure X-ray Photoelectron Spectroscopy (HP-XPS) at 150 mbar and between 150 and 350°C. The results indicate two temperature regimes; the first one with temperature dependent desorption of carbon species between 150°C and 200°C. The second temperature regime is between 250 and 350 °C. In this interval, the carbon species are formed and immediately reacted away, resulting in a lower temperature dependence on surface coverage. The XPS coverage calculations and the component analysis indicate that water is the most abundant surface adsorbate, and that CHx fragments and CO are the most abundant carbon species. The hydrogenation state of the CHx species varies with temperature, where higher temperatures result in a larger population of more hydrogenated species.
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| 19. |
- Diesen, Elias, et al.
(författare)
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Ultrafast Adsorbate Excitation Probed with Subpicosecond-Resolution X-Ray Absorption Spectroscopy
- 2021
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Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 127:1
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Tidskriftsartikel (refereegranskat)abstract
- We use a pump-probe scheme to measure the time evolution of the C K-edge x-ray absorption spectrum from CO/Ru(0001) after excitation by an ultrashort high-intensity optical laser pulse. Because of the short duration of the x-ray probe pulse and precise control of the pulse delay, the excitation-induced dynamics during the first picosecond after the pump can be resolved with unprecedented time resolution. By comparing with density functional theory spectrum calculations, we find high excitation of the internal stretch and frustrated rotation modes occurring within 200 fs of laser excitation, as well as thermalization of the system in the picosecond regime. The ∼100 fs initial excitation of these CO vibrational modes is not readily rationalized by traditional theories of nonadiabatic coupling of adsorbates to metal surfaces, e.g., electronic frictions based on first order electron-phonon coupling or transient population of adsorbate resonances. We suggest that coupling of the adsorbate to nonthermalized electron-hole pairs is responsible for the ultrafast initial excitation of the modes.
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| 20. |
- Goodwin, Christopher M., et al.
(författare)
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The Structure of the Active Pd State During Catalytic Carbon Monoxide Oxidization
- 2021
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Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 12:18, s. 4461-4465
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Tidskriftsartikel (refereegranskat)abstract
- Using grazing incidence X-rays and X-ray photoelectron spectroscopy during the mass transfer limited catalytic oxidation of CO, the long-range surface structure of Pd(100) was investigated. Under the reaction conditions of 50:4 O-2 to CO, 300 mbar pressure, and temperatures between 200 and 450 degrees C, the surface structure resulting from oxidation and the subsequent oxide reduction was elucidated. The reduction cycle was halted, and while under reaction conditions, angle-dependent X-ray photoelectron spectroscopy close to the critical angle of Pd and modeling of the data was performed. Two proposed models for the system were compared. The suggestion with the metallic islands formed on top of the oxide island was shown to be consistent with the data.
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| 21. |
- Görlin, Mikaela, et al.
(författare)
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Key activity descriptors of nickel-iron oxygen evolution electrocatalysts in the presence of alkali metal cations
- 2020
-
Ingår i: Nature Communications. - : Springer Nature. - 2041-1723. ; 11:1
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Tidskriftsartikel (refereegranskat)abstract
- Efficient oxygen evolution reaction (OER) electrocatalysts are pivotal for sustainable fuel production, where the Ni-Fe oxyhydroxide (OOH) is among the most active catalysts for alkaline OER. Electrolyte alkali metal cations have been shown to modify the activity and reaction intermediates, however, the exact mechanism is at question due to unexplained deviations from the cation size trend. Our X-ray absorption spectroelectrochemical results show that bigger cations shift the Ni2+/(3+delta)+ redox peak and OER activity to lower potentials (however, with typical discrepancies), following the order CsOH>NaOH approximate to KOH>RbOH>LiOH. Here, we find that the OER activity follows the variations in electrolyte pH rather than a specific cation, which accounts for differences both in basicity of the alkali hydroxides and other contributing anomalies. Our density functional theory-derived reactivity descriptors confirm that cations impose negligible effect on the Lewis acidity of Ni, Fe, and O lattice sites, thus strengthening the conclusions of an indirect pH effect. It is commonly accepted that electrolyte alkali metal cations modify the catalytic activity for oxygen evolution reaction. Here the authors challenge this assumption, showing that the activity is actually affected by a change in the electrolyte pH rather than a specific alkali cation.
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| 22. |
- Kapilashrami, Mukes, et al.
(författare)
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Understanding the magnetic interaction between intrinsic defects and impurity ions in room-temperature ferromagnetic Mg1-xFexO thin films
- 2016
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Ingår i: Journal of Physics. - : IOP Publishing. - 0953-8984 .- 1361-648X. ; 28:15
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Tidskriftsartikel (refereegranskat)abstract
- Understanding the nature and characteristics of the intrinsic defects and impurities in the dielectric barrier separating the ferromagnetic electrodes in a magnetic tunneling junction is of great importance for understanding the often observed 'barrier-breakdown' therein. In this connection, we present herein systematic experimental (SQUID and synchrotron-radiation-based x-ray absorption spectroscopy) and computational studies on the electronic and magnetic properties of Mg1-xFexO thin films. Our studies reveal: (i) defect aggregates comprised of basic and trimer units (Fe impurity coupled to 1 or 2 Mg vacancies) and (ii) existence of two competing magnetic orders, defect- and dopant-induced, with spin densities aligning anti-parallel if the trimer is present in the oxide matrix. These findings open up new avenues for designing tunneling barriers with high endurance and tunneling effect upon tuning the concentration/distribution of the two magnetic orders.
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| 23. |
- Koroidov, Sergey, et al.
(författare)
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Chemisorbed oxygen or surface oxides steer the selectivity in Pd electrocatalytic propene oxidation observed by operando Pd L-edge X-ray absorption spectroscopy
- 2021
-
Ingår i: Catalysis Science & Technology. - : Royal Society of Chemistry (RSC). - 2044-4753 .- 2044-4761. ; 11:10, s. 3347-3352
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Tidskriftsartikel (refereegranskat)abstract
- Controlled electrochemical oxidation of hydrocarbons to desired products is an attractive approach in catalysis. Here we study the electrochemical propene oxidation under operando conditions using Pd L-edge X-ray absorption spectroscopy (XAS) as a sensitive probe to elucidate surface processes occurring during catalysis. Together with ab initio multiple-scattering calculations, our XAS results enable assignment of characteristic changes of the Pd L-edge intensity and energy position in terms of a mechanistic understanding of the selective oxidation of propene. The results, supported by electrochemical density functional theory DFT simulations, show that in the potential range of 0.8–1.0 V vs. the reversible hydrogen electrode (RHE), selective oxidation of propene to acrolein and acrylic acid occurs on the metallic Pd surface. These reactions are proposed to proceed via the Langmuir–Hinshelwood mechanism. In contrast, for the potential range of 1.1–1.3 V vs. RHE, selective oxidation of propene to propylene glycol takes place on a Pd oxide surface.
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| 24. |
- LaRue, Jerry, et al.
(författare)
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Symmetry-resolved CO desorption and oxidation dynamics on O/Ru(0001) probed at the C K-edge by ultrafast x-ray spectroscopy
- 2022
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 157:16
-
Tidskriftsartikel (refereegranskat)abstract
- We report on carbon monoxide desorption and oxidation induced by 400 nm femtosecond laser excitation on the O/Ru(0001) surface probed by time-resolved x-ray absorption spectroscopy (TR-XAS) at the carbon K-edge. The experiments were performed under constant background pressures of CO (6 × 10−8 Torr) and O2 (3 × 10−8 Torr). Under these conditions, we detect two transient CO species with narrow 2π* peaks, suggesting little 2π* interaction with the surface. Based on polarization measurements, we find that these two species have opposing orientations: (1) CO favoring a more perpendicular orientation and (2) CO favoring a more parallel orientation with respect to the surface. We also directly detect gas-phase CO2 using a mass spectrometer and observe weak signatures of bent adsorbed CO2 at slightly higher x-ray energies than the 2π* region. These results are compared to previously reported TR-XAS results at the O K-edge, where the CO background pressure was three times lower (2 × 10−8 Torr) while maintaining the same O2 pressure. At the lower CO pressure, in the CO 2π* region, we observed adsorbed CO and a distribution of OC–O bond lengths close to the CO oxidation transition state, with little indication of gas-like CO. The shift toward “gas-like” CO species may be explained by the higher CO exposure, which blocks O adsorption, decreasing O coverage and increasing CO coverage. These effects decrease the CO desorption barrier through dipole–dipole interaction while simultaneously increasing the CO oxidation barrier.
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| 25. |
- Lömker, Patrick, et al.
(författare)
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Operando XPS and SXRD study of the Fischer-Tropsch reaction on flat and stepped Co at up to around 1 bar
-
Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- The Fischer-Tropsch catalytic reaction on Co has still several unknows regarding the surface chemical state of the catalyst and presence of various adsorbed intermediates appearing under operando conditions. Here, we report an operando X-ray photoelectron spectroscopy study of the flat Co(0001) and stepped Co(10-14) model catalyst surfaces during Fischer-Tropsch synthesis conditions at 150 mbar – 975 mbar pressure and 406 K – 548 K temperature in a H2/CO gas mixture using X-ray photoelectron spectroscopy as well surface X-ray diffraction. We observe that the Co surface remains metallic at all conditions with only adsorbed species. There are a number of different intermediates on the surface such as adsorbed CO in only on-top position, C/-CH intermediates, -CH2- species and various longer hydrocarbon molecules. The coverage of the hydrocarbon species decreases with increasing temperature but increase strongly with pressure. The stepped surface shows a significant increase in adsorbed hydrocarbon species which is a clear indication of higher reactivity. There is no observation of any CHO or CH2O species indicating a direct CO dissociation pathway and that to our observation only hydrocarbon species participate in the chain growth. The relative high coverage of CO that is almost constant for the various conditions points to that CO dissociation is one of the rate-limiting steps. The rapid increase in the coverage of hydrocarbon species at high pressure conditions and on the stepped surface further indicates that the final hydrogen induced termination step is also rate-limiting. By following the time dependence of the C 1s region with rapid change in the flow of reactants, we demonstrate that the surface species are highly dynamic resulting in delays in reaching steady-state conditions.
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| 26. |
- Schreck, Simon, et al.
(författare)
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Atom-Specific Probing of Electron Dynamics in an Atomic Adsorbate by Time-Resolved X-Ray Spectroscopy
- 2022
-
Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 129:27
-
Tidskriftsartikel (refereegranskat)abstract
- The electronic excitation occurring on adsorbates at ultrafast timescales from optical lasers that initiate surface chemical reactions is still an open question. Here, we report the ultrafast temporal evolution of x-ray absorption spectroscopy (XAS) and x-ray emission spectroscopy (XES) of a simple well-known adsorbate prototype system, namely carbon (C) atoms adsorbed on a nickel [Ni(100)] surface, following intense laser optical pumping at 400 nm. We observe ultrafast (∼100 fs) changes in both XAS and XES showing clear signatures of the formation of a hot electron-hole pair distribution on the adsorbate. This is followed by slower changes on a few picoseconds timescale, shown to be consistent with thermalization of the complete C/Ni system. Density functional theory spectrum simulations support this interpretation.
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| 27. |
- Shipilin, Mikhail, et al.
(författare)
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In Situ Surface-Sensitive Investigation of Multiple Carbon Phases on Fe(110) in the Fischer-Tropsch Synthesis
- 2022
-
Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 12:13, s. 7609-7621
-
Tidskriftsartikel (refereegranskat)abstract
- Carbide formation on iron-based catalysts is an integral and, arguably, the most important part of the Fischer–Tropsch synthesis process, converting CO and H2 into synthetic fuels and numerous valuable chemicals. Here, we report an in situ surface-sensitive study of the effect of pressure, temperature, time, and gas feed composition on the growth dynamics of two distinct iron–carbon phases with the octahedral and trigonal prismatic coordination of carbon sites on an Fe(110) single crystal acting as a model catalyst. Using a combination of state-of-the-art X-ray photoelectron spectroscopy at an unprecedentedly high pressure, high-energy surface X-ray diffraction, mass spectrometry, and theoretical calculations, we reveal the details of iron surface carburization and product formation under semirealistic conditions. We provide a detailed insight into the state of the catalyst’s surface in relation to the reaction.
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| 28. |
- Wang, Hsin-Yi, et al.
(författare)
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Direct Evidence of Subsurface Oxygen Formation in Oxide-Derived Cu by X-ray Photoelectron Spectroscopy
- 2022
-
Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 61:3
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Tidskriftsartikel (refereegranskat)abstract
- Subsurface oxygen has been proposed to be crucial in oxide-derived copper (OD-Cu) electrocatalysts for enhancing the binding of CO intermediates during CO2 reduction reaction (CO2RR). However, the presence of such oxygen species under reductive conditions still remains debated. In this work, the existence of subsurface oxygen is validated by grazing incident hard X-ray photoelectron spectroscopy, where OD-Cu was prepared by reduction of Cu oxide with H2 without exposing to air. The results suggest two types of subsurface oxygen embedded between the fully reduced metallic surface and the Cu2O buried beneath: (i) oxygen staying at lattice defects and/or vacancies in the surface-most region and (ii) interstitial oxygen intercalated in metal structure. This study adds convincing support to the presence of subsurface oxygen in OD-Cu, which previously has been suggested to play an important role to mitigate the σ-repulsion of Cu for CO intermediates in CO2RR.
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| 29. |
- Wang, Hsin-Yi, et al.
(författare)
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Time-resolved observation of transient precursor state of CO on Ru(0001) using carbon K-edge spectroscopy
- 2020
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - 1463-9076 .- 1463-9084. ; 22:5, s. 2677-2684
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Tidskriftsartikel (refereegranskat)abstract
- The transient dynamics of carbon monoxide (CO) molecules on a Ru(0001) surface following femtosecond optical laser pump excitation has been studied by monitoring changes in the unoccupied electronic structure using an ultrafast X-ray free-electron laser (FEL) probe. The particular symmetry of perpendicularly chemisorbed CO on the surface is exploited to investigate how the molecular orientation changes with time by varying the polarization of the FEL pulses. The time evolution of spectral features corresponding to the desorption precursor state was well distinguished due to the narrow line-width of the C K-edge in the X-ray absorption (XA) spectrum, illustrating that CO molecules in the precursor state rotated freely and resided on the surface for several picoseconds. Most of the CO molecules trapped in the precursor state ultimately cooled back down to the chemisorbed state, while we estimate that ∼14.5 ± 4.9% of the molecules in the precursor state desorbed into the gas phase. It was also observed that chemisorbed CO molecules diffused over the metal surface from on-top sites toward highly coordinated sites. In addition, a new “vibrationally hot precursor” state was identified in the polarization-dependent XA spectra.
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