| 1. |
- Hejral, U., et al.
(författare)
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Composition-Dependent Alloy Nanoparticle Shape Changes under Reaction Conditions : Kinetic and Thermodynamic Effects
- 2024
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Ingår i: The Journal of Physical Chemistry C. - 1932-7447 .- 1932-7455. ; 128:10, s. 4330-4342
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Tidskriftsartikel (refereegranskat)abstract
- Particle sintering and reshaping constitute the main cause for catalyst deactivation. An atomic-scale understanding of the correlation among the catalyst structure, its support, and the gas phase under realistic reaction conditions is required for its suppression. In this study, we combined high-energy grazing incidence X-ray diffraction, in situ mass spectrometry, ex situ scanning electron microscopy, and density functional theory calculations to unravel the driving force behind the composition-dependent particle shape changes and sintering processes of alpha-Al2O3(0001)-supported Pt-Pd alloy nanoparticles under realistic reaction conditions for CO oxidation. We find that pure Pt and Pt-rich particles, initially kinetically trapped in metastable flat particle shapes, undergo a strong reaction-induced height increase to adopt a more stable, theoretically predicted compact equilibrium shape. Contrarily, Pd-rich particles prove to be more resistant against shape changes, since they exhibit already a shape close to equilibrium. We thus conclude that the observed initial deviations in particle shape from the theoretical predictions are due to kinetic limitations during growth. Our data provide information on the segregation state of the alloy particles, indicating a Pt core and Pd shell structure under strongly reducing conditions and the alloying of Pt and Pd under the reaction conditions for CO oxidation close to stoichiometry.
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| 2. |
- Hejral, U., et al.
(författare)
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High-energy x-ray diffraction from surfaces and nanoparticles
- 2017
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Ingår i: Physical Review B. - 2469-9950. ; 96:19
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Tidskriftsartikel (refereegranskat)abstract
- High-energy surface-sensitive x-ray diffraction (HESXRD) is a powerful high-energy photon technique (E > 70 keV) that has in recent years proven to allow a fast data acquisition for the 3D structure determination of surfaces and nanoparticles under in situ and operando conditions. The use of a large-area detector facilitates the direct collection of nearly distortion-free diffraction patterns over a wide q range, including crystal truncation rods perpendicular to the surface and large-area reciprocal space maps from epitaxial nanoparticles, which is not possible in the conventional low-photon energy approach (E=10-20keV). Here, we present a comprehensive mathematical approach, explaining the working principle of HESXRD for both single-crystal surfaces and epitaxial nanostructures on single-crystal supports. The angular calculations used in conventional crystal truncation rod measurements at low-photon energies are adopted for the high-photon-energy regime, illustrating why and to which extent large reciprocal-space areas can be probed in stationary geometry with fixed sample rotation. We discuss how imperfections such as mosaicity and finite domain size aid in sampling a substantial part of reciprocal space without the need of rotating the sample. An exact account is given of the area probed in reciprocal space using such a stationary mode, which is essential for in situ or operando time-resolved experiments on surfaces and nanostructures.
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| 3. |
- Albertin, S., et al.
(författare)
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Surface optical reflectance combined with x-ray techniques during gas-surface interactions
- 2020
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Ingår i: Journal of Physics D. - : Institute of Physics (IOP). - 0022-3727 .- 1361-6463. ; 53:22
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Tidskriftsartikel (refereegranskat)abstract
- High energy surface x-ray diffraction (HESXRD), x-ray reflectivity (XRR), mass spectrometry (MS) and surface optical reflectance (SOR) have been combined to simultaneously obtain sub-second information on the surface structure and morphology from a Pd(100) model catalyst during in situ oxidation at elevated temperatures and pressures resulting in Pd bulk oxide formation. The results show a strong correlation between the HESXRD and SOR signal intensities during the experiment, enabling phase determination and a time-resolved thickness estimation of the oxide by HESXRD, complemented by XRR measurements. The experiments show a remarkable sensitivity of the SOR to changes in the surface phase and morphology, in particular to the initial stages of oxidation/reduction. The data imply that SOR can detect the formation of an ultrathin PdO surface oxide layer of only 2-3 angstrom thickness.
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| 4. |
- Hejral, U., et al.
(författare)
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Identification of a Catalytically Highly Active Surface Phase for CO Oxidation over PtRh Nanoparticles under Operando Reaction Conditions
- 2018
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Ingår i: Physical Review Letters. - 0031-9007. ; 120:12
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Tidskriftsartikel (refereegranskat)abstract
- Pt-Rh alloy nanoparticles on oxide supports are widely employed in heterogeneous catalysis with applications ranging from automotive exhaust control to energy conversion. To improve catalyst performance, an atomic-scale correlation of the nanoparticle surface structure with its catalytic activity under industrially relevant operando conditions is essential. Here, we present x-ray diffraction data sensitive to the nanoparticle surface structure combined with in situ mass spectrometry during near ambient pressure CO oxidation. We identify the formation of ultrathin surface oxides by detecting x-ray diffraction signals from particular nanoparticle facets and correlate their evolution with the sample's enhanced catalytic activity. Our approach opens the door for an in-depth characterization of well-defined, oxide-supported nanoparticle based catalysts under operando conditions with unprecedented atomic-scale resolution.
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| 5. |
- Martin, R, et al.
(författare)
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High-Resolution X-ray Photoelectron Spectroscopy of an IrO2(110) Film on Ir(100)
- 2020
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Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 11:17, s. 7184-7189
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Tidskriftsartikel (refereegranskat)abstract
- High-resolution X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) were used to characterize IrO2(110) films on Ir(100) with stoichiometric as well as OH-rich terminations. Core-level Ir 4f and O 1s peaks were identified for the undercoordinated Ir and O atoms and bridging and on-top OH groups at the IrO2(110) surfaces. Peak assignments were validated by comparison of the core-level shifts determined experimentally with those computed using DFT, quantitative analysis of the concentrations of surface species, and the measured variation of the Ir 4f peak intensities with photoelectron kinetic energy. We show that exposure of the IrO2(110) surface to O2 near room temperature produces a large quantity of on-top OH groups because of reaction of background H2 with the surface. The peak assignments made in this study can serve as a foundation for future experiments designed to utilize XPS to uncover atomic-level details of the surface chemistry of IrO2(110).
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| 6. |
- Pfaff, S., et al.
(författare)
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Combining high-energy X-ray diffraction with Surface Optical Reflectance and Planar Laser Induced Fluorescence for operando catalyst surface characterization
- 2019
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Ingår i: Review of Scientific Instruments. - : AIP Publishing. - 0034-6748 .- 1089-7623. ; 90:3
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Tidskriftsartikel (refereegranskat)abstract
- We have combined three techniques, High Energy Surface X-Ray Diffraction (HESXRD), Surface Optical Reflectance, and Planar Laser Induced Fluorescence in an operando study of CO oxidation over a Pd(100) catalyst. We show that these techniques provide useful new insights such as the ability to verify that the finite region being probed by techniques such as HESXRD is representative of the sample surface as a whole. The combination is also suitable to determine when changes in gas composition or surface structure and/or morphology occur and to subsequently correlate them with high temporal resolution. In the study, we confirm previous results which show that the Pd(100) surface reaches high activity before an oxide can be detected. Furthermore, we show that the single crystal catalyst surface does not behave homogeneously, which we attribute to the surface being exposed to inhomogeneous gas conditions in mass transfer limited scenarios.
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| 7. |
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