| 1. |
- Chung, Simon, et al.
(författare)
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Transient heating of Pd nanoparticles studied by x-ray diffraction with time of arrival photon detection
- 2024
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Ingår i: Structural Dynamics. - : AIP Publishing. - 2329-7778. ; 11:4
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Tidskriftsartikel (refereegranskat)abstract
- Pulsed laser heating of an ensemble of Pd nanoparticles, supported by a MgO substrate, is studied by x-ray diffraction. By time-resolved Bragg peak shift measurements due to thermal lattice expansion, the transient temperature of the Pd nanoparticles is determined, which quickly rises by at least 100 K upon laser excitation and then decays within 90 ns. The diffraction experiments were carried out using a Cu x-ray tube, giving continuous radiation, and the hybrid pixel detector Timepix3 operating with single photon counting in a time-of-arrival mode. This type of detection scheme does not require time-consuming scanning of the pump-probe delay. The experimental time resolution is estimated at 15 +/- 5 ns, which is very close to the detector's limit and matches with the 7 ns laser pulse duration. Compared to bulk metal single crystals, it is discussed that the maximum temperature reached by the Pd nanoparticles is higher and their cooling rate is lower. These effects are explained by the oxide support having a lower heat conductivity.
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| 2. |
- Gleißner, Robert, et al.
(författare)
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Role of Oxidation–Reduction Dynamics in the Application of Cu/ZnO-Based Catalysts
- 2023
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Ingår i: ACS Applied Nano Materials. - 2574-0970. ; 6:9, s. 8004-8016
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Tidskriftsartikel (refereegranskat)abstract
- We investigated Cu nanoparticles (NPs) on vicinal and basal ZnO supports to obtain an atomistic picture of the catalyst’s structure under in situ oxidizing and reducing conditions. The Cu/ZnO model catalysts were investigated at elevated gas pressures by high energy grazing incidence X-ray diffraction and ambient pressure X-ray photoelectron spectroscopy (AP-XPS). We find that the Cu nanoparticles are fully oxidized to Cu2O under atmospheric conditions at room temperature. As the nanoparticles swell during oxidation, they maintain their epitaxy on basal ZnO (000 ± 1) surfaces, whereas on the vicinal ZnO (101̅4) surface, the nanoparticles undergo a coherent tilt. We find that the oxidation process is fully reversible under H2 flow at 500 K, resulting in predominantly well-aligned nanoparticles on the basal surfaces, whereas the orientation of Cu NPs on vicinal ZnO was only partially restored. The analysis of the substrate crystal truncation rods evidences the stability of basal ZnO surfaces under all gas conditions. No Cu–Zn bulk alloy formation is observed. Under CO2 flow, no diffraction signal from the nanoparticles is detected, pointing to their completely disordered state. The AP-XPS results are in line with the formation of CuO. Scanning electron microscopy images show that massive mass transport has set in, leading to the formation of larger agglomerates.
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| 3. |
- Grånäs, Elin, et al.
(författare)
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Role of hydroxylation for the atomic structure of a non-polar vicinal zinc oxide
- 2021
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Ingår i: Communications Chemistry. - : Springer Science and Business Media LLC. - 2399-3669. ; 4:1
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Tidskriftsartikel (refereegranskat)abstract
- From the catalytic, semiconducting, and optical properties of zinc oxide (ZnO) numerous potential applications emerge. For the physical and chemical properties of the surface, under-coordinated atoms often play an important role, necessitating systematic studies of their influence. Here we study the vicinal ZnO(10 1 ¯ 4) surface, rich in under-coordinated sites, using a combination of several experimental techniques and density functional theory calculations. We determine the atomic-scale structure and find the surface to be a stable, long-range ordered, non-polar facet of ZnO, with a high step-density and uniform termination. Contrary to an earlier suggested nano-faceting model, a bulk termination fits much better to our experimental observations. The surface is further stabilized by dissociatively adsorbed H2O on adjacent under-coordinated O- and Zn-atoms. The stabilized surface remains highly active for water dissociation through the remaining under-coordinated Zn-sites. Such a vicinal oxide surface is a prerequisite for future adsorption studies with atomically controlled local step and terrace geometry.
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| 4. |
- Hartl, Tobias, et al.
(författare)
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Carbon Embedding of Pt Cluster Superlattices Templated by Hexagonal Boron Nitride on Ir(111)
- 2021
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 125:42, s. 23435-23444
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Tidskriftsartikel (refereegranskat)abstract
- With the goal to delevop the fabrication of a new type of Pt-nanoparticle carbon-support electrocatalyst, we investigate the carbon embedding of Pt cluster superlattices grown on the moiré of a monolayer of hexagonal boron nitride (h-BN) on Ir(111). Our combined scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) study establishes conformal C embedding of the Pt clusters on h-BN/Ir(111) without deterioration of superlattice order, preferential and strong binding of the embedding carbon to the Pt clusters, and upon annealing the formation of a homogeneous amorphous carbon (a-C) matrix. There are indications that while the a-C matrix and the Pt clusters bind strongly to each other, upon annealing both weaken their binding to h-BN.
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| 5. |
- 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
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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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| 6. |
- Weber, Tim, et al.
(författare)
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Extraordinary Stability of IrO2(110) Ultrathin Films Supported on TiO2(110) under Cathodic Polarization
- 2020
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Ingår i: Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; , s. 9057-9062
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Tidskriftsartikel (refereegranskat)abstract
- Down to a cathodic potentials of -1.20 V versus the reversible hydrogen electrode, the structure of IrO2(110) electrodes supported by TiO2(110) is found to be stable by in situ synchrotron-based X-ray diffraction. Such high cathodic potentials should lead to reduction to metallic Ir (Pourbaix diagram). From the IrO2 lattice parameters, determined during cathodic polarization in a H2SO4 electrolyte solution (pH 0.4), it is estimated that the unit cell volume increases by 1% due likely to proton incorporation, which is supported by the lack of significant swelling of the IrO2(110) film derived from X-ray reflectivity experiments. Ex situ X-ray photoelectron spectroscopy suggests that protons are incorporated into the IrO2(110) lattice below -1.0 V, although Ir remains exclusively in the IV+ oxidation state down to -1.20 V. Obviously, further hydrogenation of the lattice oxygen of IrO2(110) toward water is suppressed for kinetic reasons and hints at a rate-determining chemical step that cannot be controlled by the electrode potential.
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| 7. |
- Weber, Tim, et al.
(författare)
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In situ studies of the cathodic stability of single-crystalline IrO2(110) ultrathin films supported on RuO2(110)/Ru(0001) in an acidic environment
- 2020
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Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 22:40, s. 22956-22962
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Tidskriftsartikel (refereegranskat)abstract
- We investigate with in situ surface X-ray diffraction (SXRD) and X-ray reflectivity (XRR) experiments the cathodic stability of an ultrathin single-crystalline IrO2(110) film with a regular array of mesoscopic rooflike structures that is supported on a RuO2(110)/Ru(0001) template. It turns out that the planarity of the single-crystalline IrO2(110) film is lost in that IrO2(110) oxide domains delaminate at a cathodic potential of -0.18 V. Obviously, the electrolyte solution is able to reach the RuO2(110) layer presumably through the surface grain boundaries of the IrO2(110) layer. Subsequently, the single-crystalline RuO2(110) structure-directing template is reduced to amorphous hydrous RuO2, with the consequence that the IrO2(110) film loses partly its adhesion to the template. From in situ XRR experiments we find that the IrO2(110) film does not swell upon cathodic polarization down to -0.18 V, while from in situ SXRD experiments, the lattice constants of IrO2(110) are shown to be not affected. The rooflike mesostructure of the IrO2(110) flakes remains intact after cathodic polarization to -0.18 V, evidencing that the crystallinity of IrO2(110) is retained. This journal is
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| 8. |
- Weber, Tim, et al.
(författare)
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In Situ Synchrotron-Based Studies of IrO2(110)-TiO2(110) under Harsh Acidic Water Splitting Conditions : Anodic Stability and Radiation Damages
- 2022
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 126:48, s. 20243-20250
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Tidskriftsartikel (refereegranskat)abstract
- In situ stability studies of an IrO2(110)-TiO2(110) model electrode are carried out under acidic water electrolysis conditions, employing synchrotron-based techniques including surface X-ray diffraction (SXRD) and X-ray reflectometry (XRR) with a photon energy of 21.5 keV. These experiments are complemented by ex situ scanning electron microscopy (SEM), scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS) experiments. Even at an anodic current density of 250 mA·cm-2during electrochemical water splitting, the IrO2(110)-TiO2(110) model electrode turned out to be stable against Ir dissolution. However, radiation-induced damages of the IrO2(110) film are observed: Part of the IrO2(110) film delaminates upon heavy exposure to the synchrotron beam, while subsequently the uncovered TiO2(110) is subject to further (photon-induced) corrosion. We propose that the X-ray photons induce oxygen vacancy formation by displacing O2-ions of TiO2from regular to interstitial sites, while the potential drop across the TiO2(110) substrate leads to a migration of interstitial O2-ions from interface toward bulk TiO2. This reduction step at the interface between IrO2(110) and TiO2(110) weakens the adhesion of the epitaxially grown IrO2(110) film to the TiO2(110) substrate so that the strained IrO2(110) film is partially delaminated. Higher X-ray photon energies of 60-90 keV mitigate this degradation process.
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| 9. |
- Weber, Tim, et al.
(författare)
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Operando Stability Studies of Ultrathin Single-Crystalline IrO2(110) Films under Acidic Oxygen Evolution Reaction Conditions
- 2021
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Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 11:20, s. 12651-12660
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Tidskriftsartikel (refereegranskat)abstract
- The anodic corrosion behavior of 50 Å thick single-crystalline IrO2(110) films supported on slightly bulk-reduced TiO2(110) single crystals is studied during acidic water splitting by a unique combination of operando techniques, namely, synchrotron-based high-energy X-ray reflectivity (XRR) and surface X-ray diffraction (SXRD) together with highly sensitive inductively coupled plasma mass spectrometry (ICP-MS). Corrosion-induced structural and morphological changes of the IrO2(110) model electrode can be followed on the atomic scale by operando XRR and SXRD that are supplemented with ex situ scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS), whereas with ICP-MS, the corrosion rate can be quantified down to 1 pg·cm-2·s-1 with a time resolution on the second scale. The operando synchrotron-based X-ray scattering techniques are surprisingly sensitive to Ir corrosion of about 0.10 monolayer of IrO2(110) in ∼26 h, i.e., 0.4 pg·cm-2·s-1. The present study demonstrates that single-crystalline IrO2(110) films are much more stable than hitherto expected. Although the dissolution rate is very small, ICP-MS experiments reveal a significantly higher dissolution rate than the operando high-energy XRR/SXRD experiments. These differences in dissolution rate are suggested to be due to the different modi operandi encountered in ICP-MS (dynamic) and operando XRR/SXRD experiments (steady state), a fact that may need to be considered when hydrogen production is coupled to intermittent energy sources such as renewables.
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| 10. |
- Weber, Tim, et al.
(författare)
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Potential-Induced Pitting Corrosion of an IrO2(110)-RuO2(110)/Ru(0001) Model Electrode under Oxygen Evolution Reaction Conditions
- 2019
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Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 9:7, s. 6530-6539
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Tidskriftsartikel (refereegranskat)abstract
- Sophisticated IrO2(110)-based model electrodes are prepared by deposition of a 10 nm thick single-crystalline IrO2(110) layer supported on a structure-directing RuO2(110)/Ru(0001) template, exposing a regular array of mesoscopic rooflike structures. With this model electrode together with the dedicated in situ synchrotron based techniques (SXRD, XRR) and ex situ characterization techniques (SEM, ToF-SIMS, XPS), the corrosion process of IrO2(110) in an acidic environment (pH 0.4) is studied on different length scales. Potential-induced pitting corrosion starts at 1.48 V vs SHE and is initiated at so-called surface grain boundaries, where three rotational domains of IrO2(110) meet. The most surprising result is, however, that even when the electrode potential is increased to 1.94 V vs SHE 60-70% of the IrO2 film still stays intact down to the mesoscale and atomic scale and no uniform thinning of the IrO2(110) layer is encountered. Neither flat IrO2(110) terraces nor single steps are attacked. Ultrathin single-crystalline IrO2(110) layers seem to be much more stable to anodic corrosion than hitherto expected.
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