| 1. |
- Lundgren, Edvin, et al.
(författare)
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Surface composition of clean and oxidized Pd75Ag25(100) from photoelectron spectroscopy and density functional theory calculations
- 2012
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Ingår i: Surface Science. - : Elsevier BV. - 0039-6028. ; 606:23-24, s. 1777-1782
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Tidskriftsartikel (refereegranskat)abstract
- High resolution photoelectron spectroscopy and density functional theory calculations have been used to study the composition of clean and oxidized Pd75Ag25( 100). The results for the clean surface confirm earlier reports of surface segregation by Wouda et al. (1998), where the top most layers are rich in Ag. The Pd 3d core level component from the surface region is observed at higher binding energies than the contribution from the bulk which is found to be a signature of Pd embedded in Ag. Low energy electron diffraction and scanning tunneling microscopy measurements reveal that oxidation of the Pd75Ag25(100) surface results in a (root 5 x root 5)R27 degrees-O structure similar to the one reported for Pd(100). The calculations suggest that the stable structure is a PdO(101) monolayer supported on a (100) surface rich in Ag at the interface to the stoichiometric alloy. The calculated core level shifts for the oxidized surface are in good agreement with the experimental observations.
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| 2. |
- Abb, Marcel J.S., et al.
(författare)
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Thermal Stability of Single-Crystalline IrO2(110) Layers : Spectroscopic and Adsorption Studies
- 2020
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 124:28, s. 15324-15336
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Tidskriftsartikel (refereegranskat)abstract
- The interaction of ultrathin single-crystalline IrO2(110) films with the gas phase proceeds via the coordinatively unsaturated sites (cus), in particular Ircus, the undercoordinated oxygen species on-top O (Oot) that are coordinated to Ircus, and bridging O (Obr). With the combination of different experimental techniques, such as thermal desorption spectroscopy, scanning tunneling microscopy (STM), high-resolution core-level spectroscopy (HRCLS), infrared spectroscopy, and first-principles studies employing density functional theory calculations, we are able to elucidate surface properties of single-crystalline IrO2(110). We provide spectroscopic fingerprints of the active surface sites of IrO2(110). The freshly prepared IrO2(110) surface is virtually inactive toward gas-phase molecules. The IrO2(110) surface needs to be activated by annealing to 500-600 K under ultrahigh vacuum (UHV) conditions. In the activation step, Ircus sites are liberated from on-top oxygen (Oot) and monoatomic Ir metal islands are formed on the surface, leading to the formation of a bifunctional model catalyst. Vacant Ircus sites of IrO2(110) allow for strong interaction and accommodation of molecules from the gas phase. For instance, CO can adsorb atop on Ircus and water forms a strongly bound water layer on the activated IrO2(110) surface. Single-crystalline IrO2(110) is thermally not very stable although chemically stable. Chemical reduction of IrO2(110) by extensive CO exposure at 473 K is not observed, which is in contrast to the prototypical RuO2(110) system.
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| 3. |
- Abbondanza, Giuseppe, et al.
(författare)
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Anisotropic strain variations during the confined growth of Au nanowires
- 2023
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Ingår i: Applied Physics Letters. - : AIP Publishing. - 0003-6951 .- 1077-3118. ; 122:12
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Tidskriftsartikel (refereegranskat)abstract
- The electrochemical growth of Au nanowires in a template of nanoporous anodic aluminum oxide was investigated in situ by means of grazing-incidence transmission small- and wide-angle x-ray scattering (GTSAXS and GTWAXS), x-ray fluorescence (XRF), and two-dimensional surface optical reflectance. The XRF and the overall intensity of the GTWAXS patterns as a function of time were used to monitor the progress of the electrodeposition. Furthermore, we extracted powder diffraction patterns in the direction of growth and in the direction of confinement to follow the evolution of the direction-dependent strain. Quite rapidly after the beginning of the electrodeposition, the strain became tensile in the vertical direction and compressive in the horizontal direction, which showed that the lattice deformation of the nanostructures can be artificially varied by an appropriate choice of the deposition time. By alternating sequences of electrodeposition with sequences of rest, we observed fluctuations of the lattice parameter in the direction of growth, attributed to stress caused by electromigration. Furthermore, the porous domain size calculated from the GTSAXS patterns was used to monitor how homogeneously the pores were filled.
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| 4. |
- Abbondanza, Giuseppe, 1991, et al.
(författare)
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Au-Pd Barcode Nanowires with Tailored Lattice Parameters and Segment Lengths for Catalytic Applications
- 2024
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Ingår i: ACS Applied Nano Materials. - 2574-0970. ; 7:4, s. 3861-3874
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Tidskriftsartikel (refereegranskat)abstract
- In this study, we present a systematic investigation of the controlled fabrication of Au-Pd barcode nanowires within nanoporous anodic aluminum oxide (NP-AAO) templates. By using a combination of in situ X-ray diffraction (XRD), focused ion beam scanning electron microscopy (FIB-SEM), and transmission electron microscopy (TEM), we elucidate the influence of template preparation methods on the resulting nanowire properties. The template treatment, involving either pore widening or barrier layer thinning, significantly impacts nanowire growth. Through the analysis of the XRD data, we observe sequential deposition of Au and Pd segments with lattice parameter variations and strain effects. Particularly, the lattice parameters of Au and Pd segments display intricate temporal dependencies, influenced by interfacial effects and strain caused by growth under confinement. FIB-SEM imaging reveals uniform and reproducible nanowire lengths in the template treated with pore widening. Furthermore, TEM analysis confirms the presence of distinct Au and Pd segments, while scanning TEM-energy-dispersive X-ray spectroscopy revealed minor evidence of interdiffusion between the first and the second electrodeposited segments. Our findings emphasize the potential of the electrodeposition process within nanoporous templates for producing barcode nanowires with precise segmental properties. The combination of in situ XRD and electron microscopy offers valuable insights into the growth dynamics and structural characteristics of the fabricated Au-Pd barcode nanowires. This controlled fabrication strategy opens doors to tailoring nanowire properties for diverse applications, particularly in catalysis.
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| 5. |
- Abbondanza, Giuseppe, 1991, et al.
(författare)
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Hydride formation and dynamic phase changes during template-assisted Pd electrodeposition
- 2023
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Ingår i: Nanotechnology. - 1361-6528 .- 0957-4484. ; 34:50
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Tidskriftsartikel (refereegranskat)abstract
- We investigated the structural evolution of electrochemically fabricated Pd nanowires in situ by means of grazing-incidence transmission small- and wide-angle x-ray scattering (GTSAXS and GTWAXS), x-ray fluorescence (XRF) and two-dimensional surface optical reflectance (2D-SOR). This shows how electrodeposition and the hydrogen evolution reaction (HER) compete and interact during Pd electrodepositon. During the bottom-up growth of the nanowires, we show that beta-phase Pd hydride is formed. Suspending the electrodeposition then leads to a phase transition from beta-phase Pd hydride to alpha-phase Pd. Additionally, we find that grain coalescence later hinders the incorporation of hydrogen in the Pd unit cell. GTSAXS and 2D-SOR provide complementary information on the volume fraction of the pores occupied by Pd, while XRF was used to monitor the amount of Pd electrodeposited.
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| 6. |
- Abbondanza, Giuseppe, et al.
(författare)
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Quantitative powder diffraction using a (2 + 3) surface diffractometer and an area detector
- 2021
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Ingår i: Journal of Applied Crystallography. - 1600-5767. ; 54:4, s. 1140-1152
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Tidskriftsartikel (refereegranskat)abstract
- X-ray diffractometers primarily designed for surface X-ray diffraction are often used to measure the diffraction from powders, textured materials and fiber-texture samples in 2θ scans. Unlike in high-energy powder diffraction, only a fraction of the powder rings is typically measured, and the data consist of many detector images across the 2θ range. Such diffractometers typically scan in directions not possible on a conventional laboratory diffractometer, which gives enhanced control of the scattering vector relative to the sample orientation. There are, however, very few examples where the measured intensity is directly used, such as for profile/Rietveld refinement, as is common with other powder diffraction data. Although the underlying physics is known, converting the data is time consuming and the appropriate corrections are dispersed across several publications, often not with powder diffraction in mind. This paper presents the angle calculations and correction factors required to calculate meaningful intensities for 2θ scans with a (2 + 3)-type diffractometer and an area detector. Some of the limitations with respect to texture, refraction and instrumental resolution are also discussed, as is the kind of information that one can hope to obtain.
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| 7. |
- Abbondanza, Giuseppe, et al.
(författare)
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Templated electrodeposition as a scalable and surfactant-free approach to the synthesis of Au nanoparticles with tunable aspect ratios
- 2022
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Ingår i: Nanoscale Advances. - : Royal Society of Chemistry. - 2516-0230. ; 4:11, s. 2452-2467
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Tidskriftsartikel (refereegranskat)abstract
- A high-throughput method for the fabrication of ordered arrays of Au nanoparticles is presented. It is based on pulsed electrodeposition into porous anodic alumina templates. In contrast to many synthesis routes, it is cyanide-free, prior separation of the alumina template from the aluminium substrate is not required, and the use of contaminating surfactants/capping agents often found in colloidal synthesis is avoided. The aspect ratio of the nanoparticles can also be tuned by selecting an appropriate electrodeposition time. We show how to fabricate arrays of nanoparticles, both with branched bases and with hemispherical bases. Furthermore, we compare the different morphologies produced with electron microscopies and grazing-incidence synchrotron X-ray diffraction. We find the nanoparticles are polycrystalline in nature and are compressively strained perpendicular to the direction of growth, and expansively strained along the direction of growth. We discuss how this can produce dislocations and twinning defects that could be beneficial for catalysis.
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| 8. |
- Albertin, Stefano, et al.
(författare)
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Oxidation and Reduction of Ir(100) Studied by High-Energy Surface X-ray Diffraction
- 2022
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 126:11, s. 5244-5255
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Tidskriftsartikel (refereegranskat)abstract
- The oxidation and reduction of an Ir(100) surface using 2.5, 5, and 10 mbar O2 partial pressure and a sample temperature of 775 K have been studied by using high-energy surface X-ray diffraction (HESXRD) which allowed to record large volumes of reciprocal space in short time periods. The complex 3D diffraction patterns could be disentangled in a stepwise procedure. For the 2.5mbar experiment the measurements indicate the formation of an Ir(100)-O c(2 × 2) oxygen superstructure along with the onset of epitaxial IrO2(110) bulk oxide formation. For the 5 and 10 mbar O2 partial pressures the formation of additional IrO2 bulk oxide epitaxies with (100) and (101) orientations as well as of polycrystalline IrO2 was observed. Upon CO reduction, we found the IrO2 islands to be reduced into epitaxial and metallic Ir(111) and (221) oriented islands.
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| 9. |
- Andersen, Jesper N., et al.
(författare)
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Core level binding energy shifts in interfaces between 4d and alkali metals
- 1995
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Ingår i: Journal of Electron Spectroscopy and Related Phenomena. - : Elsevier BV. - 0368-2048. ; 75:C, s. 225-232
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Tidskriftsartikel (refereegranskat)abstract
- High resolution core level photoemission measurements are reported of the binding energy shifts of the 3d core level of Mo, Rh and Pd atoms in interfaces between these 4d metals and alkali metals. The core level binding energies of the interface 4d atoms are found to be almost equal to those of the clean surface atoms for Mo and Rh. For Pd a large alkali induced shift towards higher binding energy is found. The implications of these results for the information derivable from core level binding energy shifts in metallic interfaces are discussed and it is demonstrated that the present results are explained by established total energy based models for core level binding energy shifts in metallic systems.
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| 10. |
- Arman, Alif, et al.
(författare)
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Adsorption of hydrogen on stable and metastable Ir(100) surfaces
- 2017
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Ingår i: Surface Science. - : Elsevier BV. - 0039-6028. ; 656, s. 66-76
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Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- Using the combination of high resolution core level spectroscopy and density functional theory we present adetailed spectroscopic study for all clean and hydrogen covered phases of Ir(100). The results are complementedby an investigation of the hydrogen desorption process from various phases using temperature programmeddesorption spectroscopy and scanning tunneling microscopy. In total, all experimentally determined core levelshifts match very well with those predicted by density functional theory based on established structural models.In particular, we find for the (bridge site) adsorption on the unreconstructed 1×1 phase that the initial core levelshift of surface Ir atoms is altered by +0.17 eV for each Ir–H bond formed. In the submonolayer regime we findevidence for island formation at low temperatures. For the H-induced deconstructed 5×1-H phase we identifyfour different surface core level shifts with two of them being degenerate. Finally, for the reconstructed 5×1-hexphase also four surface components are identified, which undergo a rather rigid core level shift of +0.15 eV uponhydrogen adsorption suggesting a similarly homogeneous charge transfer to all Ir surface atoms.Thermodesorption experiments for the 5×1-H phase reveal two different binding states for hydrogenindependent of the total coverage. We conclude that the surface always separates into patches of fully covereddeconstructed and uncovered reconstructed phases. We could also show by tunneling microscopy that with thedesorption of the last hydrogen atom from the deconstructed unit cell the surface instantaneously reverts intothe reconstructed state. Eventually, we could determine the saturation coverage upon molecular adsorption forall phases to be θmax = 1.0 ML1×1−H , θ = 0.8 ML max5×1−H , and θ ≥ 1.0 ML max5×1−hex−H .
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