| 1. |
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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. |
- Abbas, Zareen, 1962, et al.
(författare)
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Size-Dependent Surface Charging of Nanoparticles
- 2008
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Ingår i: J of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 112:15, s. 5715-5723
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Tidskriftsartikel (refereegranskat)abstract
- Experimental interest in the possible curvature dependence of particle charging in electrolyte solutions is subjected to theoretical analysis. The corrected Debye-Hückel theory of surface complexation (CDH-SC) and Monte Carlo (MC) simulation are applied to investigate the dependence of surface charging of metal oxide nanoparticles on their size. Surface charge density versus pH curves for spherical metal oxide nanoparticles in the size range of 1-100 nm are calculated at various concentrations of a background electrolyte. The surface charge density of a nanoparticle is found to be highly size-dependent. As the particle diameter drops to below 10 nm there is considerable increase in the surface charge density as compared with the limiting values seen for particles larger than 20 nm. This increase in the surface charge density is due to the enhanced screening efficiency of the electrolyte solution around small nanoparticles, which is most prominent for particles of diameters less than 5 nm. For example, the surface charge densities calculated for 2 nm particles at 0.1 M concentration are very close to the values obtained for 100 nm particles at 1 M concentration. These predictions of the dependence of surface charge density on particle size by the CDH-SC theory are in very good agreement with the corresponding results obtained by the MC simulations. A shift in the pH value of the point of zero charge toward higher pH values is also seen with a decreasing particle size.
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| 4. |
- Abid, Jean-Pierre, et al.
(författare)
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Controlled reversible adsorption of core : Shell metallic nanoparticles at the polarized water/1,2-dichloroethane interface investigated by optical second-harmonic generation
- 2007
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 111:25, s. 8849-8855
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Tidskriftsartikel (refereegranskat)abstract
- We report the observation of the reversible adsorption of core-shell gold-silver nanoparticles at the polarized water/1,2-dichloroethane interface using the nonlinear optical technique of surface second-harmonic generation. This study unambiguously demonstrates the excellent stability against aggregation of these core-shell nanoparticles, namely, gold core nanoparticles coated with silver layers of variable thickness, in the presence of an electrolyte salt like lithium chloride. Furthermore, it is also demonstrated that the adsorption of the nanoparticles is reversible by modulating the applied potential at water/1,2-dichloroethane interface. The analysis of these results is performed within the Debye-Huckel approximation of the electrostatic interactions between the nanoparticles. This approach shows that the stability of core-shell nanoparticles can be attributed to the formation of a silver oxide layer at the Surface of the particles.
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| 5. |
- Abou-Hamad, Edy, et al.
(författare)
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Hydrogenation of C-60 in Peapods: Physical Chemistry in Nano Vessels
- 2009
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Ingår i: The Journal of Physical Chemistry C. - WASHINGTON, DC 20036 : AMER CHEMICAL SOC. - 1932-7447 .- 1932-7455. ; 113:20, s. 8583-8587
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Tidskriftsartikel (refereegranskat)abstract
- Hydrogenation of C-60 molecules inside SWNT was achieved by direct reaction with hydrogen gas at elevated pressure and temperature. Evidence for the C-60 hydrogenation in peapods is provided by isotopic engineering with specific enrichment of encapsulated species and high resolution C-13 and H-1 NMR spectroscopy with the observation of characteristic diamagnetic and paramagnetic shifts of the NMR lines and the appearance of sp(3) carbon resonances. We estimate that approximately 78% of the C-60 molecules inside SWNTs are hydrogenated to an average degree of 14 hydrogen atoms per C-60 molecule. As a consequence, the rotational dynamics of the encapsulated C60Hx molecules is clearly hindered. Our successful hydrogenation experiments open completely new roads to understand and control confined chemical reactions at the nano scale
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| 6. |
- Abrahamsson, Brita, 1989, et al.
(författare)
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NOx Adsorption on ATiO(3)(001) Perovskite Surfaces
- 2015
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 119:32, s. 18495-18503
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Tidskriftsartikel (refereegranskat)abstract
- Density functional theory calculations have been used to explore NO adsorption on perovskite oxides surfaces ATiO(3)(001) with A = Ca, Sr, Ba. NO adsorbs weakly on all facets with no apparent A-ion dependence, whereas NO2 adsorbs preferably over AO-terminated surfaces with adsorption energies that correlate with the ionization potentials of the alkaline earth atoms. Simultaneous adsorption of NO and NO2 is found to substantially enhance the stability of the adsorbates owing to an oxide mediated electron-pairing mechanism. Stabilization is also predicted for NO/O-2 adsorption, and it is suggested that the presence of oxygen favors the formation of nitrite/nitrate pairs. It is found that the NOx adsorption properties can be modified by mixing alkaline earth cations in the perovskite framework. The results are put in context by comparison with NOx adsorption on the corresponding (001) facets of alkaline earth metal oxides and TiO2(110).
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| 7. |
- Agarwal, Nisha Rani, 1987, et al.
(författare)
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Nonlinear Optical Properties of Polyynes: An Experimental Prediction for Carbyne
- 2016
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 120:20, s. 11131-11139
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Tidskriftsartikel (refereegranskat)abstract
- We present the experimental determination of the vibrational contribution to molecular second hyperpolarizability (gamma(vib)) of very long polyynes that have been recently made available thanks to progress in chemical synthesis. Based on a simple theoretical model, the available experimental data allow estimating the asymptotic behavior of the vibrational contribution to molecular hyperpolarizability for increasing chain length.
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| 8. |
- Agrios, Alexander G., et al.
(författare)
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Low-temperature TiO2 Films for Dye-sensitized Solar Cells : Factors Affecting Energy Conversion Efficiency
- 2008
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 112:27, s. 10021-10026
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Tidskriftsartikel (refereegranskat)abstract
- Semiconductor films prepd. by electrostatic layer-by-layer deposition can be used to fabricate dye-sensitized solar cells after low-temp. treatment (150 DegC). However, the resulting photocurrent is much less than when the film is sintered at 500 DegC. The difference in short-circuit current is a factor of 2.2 with the Ru-based dye N719 and is 3.5 with the org. dye D5. The photocurrent at a given wavelength is proportional to the light-harvesting efficiency, charge injection effciency, and charge collection efficiency. Sintered films take up more than 60% more of either dye than unsintered films and therefore absorb more photons. Electron injection is hindered in unsintered films due to a conduction band edge potential 100 mV more neg. than in a sintered electrode. Addnl. injection effects could be due to adsorption of the dye to polymer rather than to TiO2 in unsintered films, although our measurements were inconclusive on this point. Kinetic studies show electron transport times (ttr) an order of magnitude faster then electron lifetimes (te) in both sintered and unsintered electrodes. Furthermore, a Li+ insertion expt. shows that both films have good elec. connectivity between TiO2 nanoparticles. Unsintered films thus exhibit efficient charge transport despite the presence of polymer and the lack of heat treatment to induce necking.
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| 9. |
- Aharony, A., et al.
(författare)
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Effects of Different Lead Magnetizations on the Datta-Das Spin Field-Effect Transistor
- 2019
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 123:17, s. 11094-11100
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Tidskriftsartikel (refereegranskat)abstract
- A Datta-Das spin field-effect transistor is built of a one-dimensional weak link, with Rashba spin-orbit interactions (SOIs), which connects two magnetized reservoirs. The particle and spin currents between the two reservoirs are calculated to lowest order in the tunneling through the weak link and in the wide-band approximation, with emphasis on their dependence on the origins of the "bare" magnetizations in the reservoirs. The SOI is found to generate magnetization components in each reservoir, which rotate in the plane of the electric field (generating the SOI) and the weak link, only if the "bare" magnetization of the other reservoir has a nonzero component in that plane. The SOI affects the charge current only if both reservoirs are polarized. The charge current is conserved, but the transverse rotating magnetization current is not conserved because the SOI in the weak link generates extra spin polarizations which are injected into the reservoirs.
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| 10. |
- Ahlund, John, et al.
(författare)
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Molecular growth determined by surface domain patterns
- 2008
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 112:17, s. 6887-6890
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Tidskriftsartikel (refereegranskat)abstract
- The growth of iron phthalocyanine (FePc) on InSb(001) c(8 x 2) at submonolayer coverage has been investigated with scanning tunneling microscopy (STM). FePc adsorbs flat centered on the In rows both at 70 K and at room temperature (RT). However, the shapes of the two-dimensional molecular islands are fundamentally different; while the RT growth results in chainlike structures along the [I 10] direction, as already observed for other Pc's adsorbed on the same surface, the islands are prolonged along [110], i.e., perpendicular to the substrate rows, at 70 K. These observations are explained on the basis of a recently observed new surface phase at low temperature, resulting in structural domains on the surface. The molecular growth front follows the propagating domain boundary that freezes at low temperature.
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| 11. |
- Ahmad, Y., et al.
(författare)
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NMR and NEXAFS Study of Various Graphite Fluorides
- 2013
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 117:26, s. 13564-13572
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Tidskriftsartikel (refereegranskat)abstract
- Graphite fluorides with different structural types (CyF)(n) (y = 2.5, 2, and 1) and room temperature graphite fluorides were studied by solid state,NMR and NEXAFS. Data extracted from those two techniques are complementary, providing information about the C-F bonding and the hybridization character of the carbon atom valence states. The comparison of data obtained by different methods such as NMR, Raman, and X-ray absorption leads to similar conclusions regarding the chemical bonding in fluorographites. Several major configurations of fluorinated graphites are discussed, that is, planar sheets with mainly sp(2) hybridization in room temperature graphite fluorides and corrugated sheets with sp(3) hybridization in covalent high temperature graphite fluoride. Different references such as highly oriented pyrolytic graphite (HOPG), graphitized carbon nanodiscs (graph-CNDs) and nanodiamonds (NDs) have also been investigated for comparison.
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| 12. |
- Ahmed, Taha, et al.
(författare)
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Optical Quantum Confinement in Ultrasmall ZnO and the Effect of Size on Their Photocatalytic Activity
- 2020
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Ingår i: The Journal of Physical Chemistry C. - : AMER CHEMICAL SOC. - 1932-7447 .- 1932-7455. ; 124:11, s. 6395-6404
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Tidskriftsartikel (refereegranskat)abstract
- Zinc oxide is a well-known metal oxide semiconductor with a wide direct band gap that offers a promising alternative to titanium oxide in photocatalytic applications. ZnO is studied here as quantum dots (QDs) in colloidal suspensions, where ultrasmall nanoparticles of ZnO show optical quantum confinement with a band gap opening for particles below 9 nm in diameter from the shift of the band edge energies. The optical properties of growing ZnO QDs are determined with Tauc analysis, and a system of QDs for the treatment and degradation of distributed threats is analyzed using an organic probe molecule, methylene blue, whose UV/vis spectrum is analyzed in some detail. The effect of optical properties of the QDs and the kinetics of dye degradation are quantified for low-dimensional ZnO materials in the range of 3-8 nm and show a substantial increase in photocatalytic activity compared to larger ZnO particles. This is attributed to a combined effect from the increased surface area as well as a quantum confinement effect that goes beyond the increased surface area. The results show a significantly higher photocatalytic activity for the QDs between 3 and 6 nm with a complete decolorization of the organic probe molecule, while QDs from 6 nm and upward in diameter show signs of competing reduction reactions. Our study shows that ultrasmall ZnO particles have a reactivity beyond that which is expected because of their increased surface area and also demonstrates size-dependent reaction pathways, which introduces the possibility for size-selective catalysis.
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| 13. |
- Ai, Yuejie, et al.
(författare)
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Hydrophobicity and Hydrophilicity Balance Determines Shape Selectivity of Suzuki Coupling Reactions Inside Pd@meso-SiO2 Nanoreactor
- 2016
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 120:19, s. 10244-10251
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Tidskriftsartikel (refereegranskat)abstract
- Molecular sorting and catalysis directed by shape selectivity have been extensively applied in porous extended frameworks for a low-carbon, predictable, renewable component of modern industry. A comprehensive understanding of the underlying recognition mechanism toward different shapes is unfortunately still missing, owing to the lack of structural and dynamic information under operating conditions. We demonstrate here that such difficulties can be overcome by state-of-the-art molecular dynamics simulations which provide atomistic details that are not accessible experimentally, as exemplified by our interpretation for the experimentally observed aggregation induced shape selectivity for Suzuki C-C coupling reaction catalyzed by Pd particles in mesoporous silica. It is found that both aggregation ability and aggregating pattern of the reactants play the decisive role in controlling the shape selectivity, which are in turn determined by the balance between the hydrophobicity and hydrophilicity of the reactants, or in other words, by the balance between the noncovalent hydrogen bonding interaction and van der Waals forces. A general rule that allows prediction of the shape selectivity of a reactant has been proposed and verified against experiments. We show that molecular modeling is a powerful tool for rational design of new mesoporous systems and for the control of catalytic reactions that are important for the petrochemical industry.
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| 14. |
- Akola, J., et al.
(författare)
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Thiolate-Protected Au-25 Superatoms as Building Blocks: Dimers and Crystals
- 2010
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 114:38, s. 15986-15994
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Tidskriftsartikel (refereegranskat)abstract
- A particularly stable thiolate-protected gold nanocluster, Au-25(SR)(18), was structurally characterized from X-ray crystallography in 2008, and concomitantly its electronic and optical properties were analyzed via density functional theory. The robust geometry and a well-understood electronic structure of this cluster motivate explorations of properties of extended systems made out of Au-25(SR)(18) building blocks. As a first step in this direction, we analyze here structural, vibrational, electronic, and optical properties of the Au-25 cluster anion as it was observed in the crystalline environment and predict properties of cluster dimers, where the Au-25 units are linked together. via an aromatic dithiolate linker. We show that properties of each Au-25 unit of the dimer can be quite independently modified from the other by doping with a nonmagnetic (Pd) or magnetic (Mn) metal atom. We anticipate that material systems with interesting properties could be made from these building blocks, provided that a suitable chemistry for their controlled linking can be found.
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| 15. |
- Aktekin, Burak, et al.
(författare)
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Understanding the Capacity Loss in LiNi0.5Mn1.5O4-Li4Ti5O12 Lithium-Ion Cells at Ambient and Elevated Temperatures
- 2018
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 122:21, s. 11234-11248
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Tidskriftsartikel (refereegranskat)abstract
- The high-voltage spinel LiNi0.5Mn1.5O4, (LNMO) is an attractive positive electrode because of its operating voltage around 4.7 V (vs Li/Li+) and high power capability. However, problems including electrolyte decomposition at high voltage and transition metal dissolution, especially at elevated temperatures, have limited its potential use in practical full cells. In this paper, a fundamental study for LNMO parallel to Li4Ti5O12 (LTO) full cells has been performed to understand the effect of different capacity fading mechanisms contributing to overall cell failure. Electrochemical characterization of cells in different configurations (regular full cells, back-to-back pseudo-full cells, and 3-electrode full cells) combined with an intermittent current interruption technique have been performed. Capacity fade in the full cell configuration was mainly due to progressively limited lithiation of electrodes caused by a more severe degree of parasitic reactions at the LTO electrode, while the contributions from active mass loss from LNMO or increases in internal cell resistance were minor. A comparison of cell formats constructed with and without the possibility of cross-talk indicates that the parasitic reactions on LTO occur because of the transfer of reaction products from the LNMO side. The efficiency of LTO is more sensitive to temperature, causing a dramatic increase in the fading rate at 55 degrees C. These observations show how important the electrode interactions (cross-talk) can be for the overall cell behavior. Additionally, internal resistance measurements showed that the positive electrode was mainly responsible for the increase of resistance over cycling, especially at 55 degrees C. Surface characterization showed that LNMO surface layers were relatively thin when compared with the solid electrolyte interphase (SEI) on LTO. The SEI on LTO does not contribute significantly to overall internal resistance even though these films are relatively thick. X-ray absorption near-edge spectroscopy measurements showed that the Mn and Ni observed on the anode were not in the metallic state; the presence of elemental metals in the SEI is therefore not implicated in the observed fading mechanism through a simple reduction process of migrated metal cations.
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| 16. |
- Al-Shammari, Rusul M., et al.
(författare)
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Tunable Wettability of Ferroelectric Lithium Niobate Surfaces : The Role of Engineered Microstructure and Tailored Metallic Nanostructures
- 2017
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Ingår i: The Journal of Physical Chemistry C. - : AMER CHEMICAL SOC. - 1932-7447 .- 1932-7455. ; 121:12, s. 6643-6649
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Tidskriftsartikel (refereegranskat)abstract
- An important aspect of optimizing micro- and optofluidic devices for lab on -a-chip systems is the ability to engineer materials properties including surface structure and charge to control wettability. Biocompatible ferroelectric lithium niobate (LN), which is well-known for acoustic and nonlinear optical applications, has recently found potential micro- and optofluidic applications. However, the tunable wettability of such substrates has yet to be explored in detail. Here, we show that the contact angle of LN substrates can be reproducibly tailored between similar to 7 degrees and similar to 421 degrees by controlling the surface topography and chemistry at the nano- and micrometer scale via ferroelectric domain and polarization engineering and polarization-directed photoassisted deposition of metallic nanostructures.
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| 17. |
- Alarcon, Hugo, et al.
(författare)
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Modification of nanostructured TiO2 electrodes by electrochemical Al3+ insertion : Effects on dye-sensitized solar cell performance
- 2007
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 111:35, s. 13267-13274
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Tidskriftsartikel (refereegranskat)abstract
- Nanostructured TiO2 films were modified by insertion with aluminum ions using an electrochemical process. After heat treatment these films were found suitable as electrodes in dye-sensitized solar cells. By means of a catechol adsorption test, as well as photoelectron spectroscopy (PES), it was demonstrated that the density of Ti atoms at the metal oxide/electrolyte interface is reduced after Al modification. There is, however, not a complete coverage of aluminum oxide onto the TiO2, but the results rather suggest either the formation of a mixed Al-Ti oxide surface layer or formation of a partial aluminum oxide coating. No new phase could, however, be detected. In solar cells incorporating Al-modified TiO2 electrodes, both electron lifetimes and electron transport times were increased. At high concentrations of inserted aluminum ions, the quantum efficiency for electron injection was significantly decreased. Results are discussed at the hand of different models: A multiple trapping model, which can explain slower kinetics by the creation of additional traps during Al insertion, and a surface layer model, which can explain the reduced recombination rate, as well as the reduced injection efficiency, by the formation of a blocking layer.
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| 18. |
- 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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| 19. |
- Albinsson, David, 1990, et al.
(författare)
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Heterodimers for in Situ Plasmonic Spectroscopy: Cu Nanoparticle Oxidation Kinetics, Kirkendall Effect, and Compensation in the Arrhenius Parameters
- 2019
-
Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 123:10, s. 6284-6293
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Tidskriftsartikel (refereegranskat)abstract
- The ability to study oxidation, reduction, and other chemical transformations of nanoparticles in real time and under realistic conditions is a nontrivial task due to their small dimensions and the often challenging environment in terms of temperature and pressure. For scrutinizing oxidation of metal nanoparticles, visible light optical spectroscopy based on the plasmonic properties of the metal has been established as a suitable method. However, directly relying on the plasmonic resonance of metal nanoparticles as a built-in probe to track oxidation has a number of drawbacks, including the loss of optical contrast in the late oxidation stages. To address these intrinsic limitations, we present a plasmonic heterodimer-based nanospectroscopy approach, which enables continuous self-referencing by using polarized light to eliminate parasitic signals and provides large optical contrast all the way to complete oxidation. Using Au-Cu heterodimers and combining experiments with finite-difference time-domain simulations, we quantitatively analyze the oxidation kinetics of ca. 30 nm sized Cu nanoparticles up to complete oxidation. Taking the Kirkendall effect into account, we extract the corresponding apparent Arrhenius parameters at various extents of oxidation and find that they exhibit a significant compensation effect, implying that changes in the oxidation mechanism occur as oxidation progresses and the structure of the formed oxide evolves. In a wider perspective, our work promotes the use of model-system-type in situ optical plasmonic spectroscopy experiments in combination with electrodynamics simulations to quantitatively analyze and mechanistically interpret oxidation of metal nanoparticles and the corresponding kinetics in demanding chemical environments, such as in heterogeneous catalysis.
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| 20. |
- Alcantara, K. Suarez, et al.
(författare)
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3CaH(2)+4MgB(2) + CaF2 Reactive Hydride Composite as a Potential Hydrogen Storage Material: Hydrogenation and Dehydrogenation Pathway
- 2012
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 116:12, s. 7207-7212
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Tidskriftsartikel (refereegranskat)abstract
- A reactive hydride composite (RHC) with initial composition 3CaH(2) + 4MgB(2) + CaF2 was studied by in situ synchrotron radiation powder X-ray diffraction (SR-PXD) and X-ray absorption near edge structure (XANES) at the B K-edge and at the Ca K-edge. The hydrogenation reaction proceeds by an unknown intermediate. No evidence of intermediates was observed during the dehydrogenation reaction. B and Ca K-edge XANES results hint to a closed interaction of CaF2 and Ca(BH4)(2). The main function of CaF2 in the 3CaH(2) + 4MgB(2) + CaF2 RHC is as a dopant for the hydrogenation and dehydrogenation reactions.
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| 21. |
- Alegret, Joan, 1977, et al.
(författare)
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Plasmonic properties of silver trimers with trigonal symmetry fabricated by electron-beam lithography
- 2008
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 112:37, s. 14313-14317
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Tidskriftsartikel (refereegranskat)abstract
- We investigate the dipolar plasmon modes of nanoparticle trimers formed by three equal silver disks of diameter D = 100 nm located on the vertexes of an equilateral triangle. Samples were fabricated by electron-beam lithography and studied experimentally by dark-field spectroscopy. The results are found to be in good agreement with electrodynamical simulations based on the discrete dipole approximation (DDA). Similar to nanoparticle dimers, the trimer system exhibits two hybridized dipole resonances to the red and to the blue of the single particle resonance. However, the far-field spectra are polarization-insensitive for light incident normal to the plane of the trimer, and the peak shifts, which occur as the edge-to-edge distance d between the particles decrease, are smaller than for dimers. Moreover, we find that the dipolar displacement patterns are well described by linear combinations of bonding and antibonding symmetry adapted coordinates obtained through symmetry analysis based on the ideal D-3h point-group.
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| 22. |
- Ali, Ehesan, et al.
(författare)
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Tuning the Magnetic Interaction between Manganese Porphyrins and Ferromagnetic Co Substrate through Dedicated Control of the Adsorption
- 2009
-
Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 113:32, s. 14381-14383
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Tidskriftsartikel (refereegranskat)abstract
- We report, on the basis of density-functional theory+U (DFT+U) calculations that metalloporphyrins can adsorb on ferromagnetic metal surfaces in two distinct configurations. Two separate adsorption minima are obtained for manganese porphyrin (MnP) on Co from our DFT+U total energy calculations, which correspond to strong and weak adsorption strengths, respectively. By steering the nature of adsorption, we find that distinct chemical interactions as well as magnetic exchange interactions between the metalloporphyrin and the metal surface can be realized. We furthermore show that a switching of the MnP molecule's spin state can occur even for the weakly adsorbed case. This new discovery opens up prospects for engineering the chemical and magnetic exchange interaction in new functionalized spintronic materials.
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| 23. |
- Ali-Löytty, Harri, et al.
(författare)
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Chemical Dissolution of Pt(111) during Potential Cycling under Negative pH Conditions Studied by Operando X-ray Photoelectron Spectroscopy
- 2019
-
Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 123:41, s. 25128-25134
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Tidskriftsartikel (refereegranskat)abstract
- Dissolution of a platinum catalyst is a major degradation mechanism of fuel cells, but the exact reaction mechanism has remained unclear. Here, electrochemical ambient pressure X-ray photoelectron spectroscopy (EC-APXPS) was utilized to provide direct information on chemical species on a single-crystal Pt(111) electrode under extremely low pH conditions. Measurements were conducted using a novel condensed electrolyte film electrochemical cell applying work function measurement as a loss-free probe for electrochemical potential. We show that platinum can dissolve chemically as Pt2+ ion during potential cycling and redeposit as Pt2+ at the onset potential for cathodic reactions. The dissolution of Pt does not require electrochemical oxidation via oxide place exchange. In contrast, the adsorption of oxygenated species (OH* or O*) at the onset potential for anodic reactions is a sufficient prerequisite to the dissolution. These results provide new insight into the degradation mechanism of Pt under extremely low pH conditions, predicted by the Pourbaix diagram, having practical applications to the durability of Pt-based catalysts in electrochemical energy conversion devices.
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| 24. |
- Amft, Martin, et al.
(författare)
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A Molecular Mechanism for the Water-Hydroxyl Balance during Wetting of TiO2
- 2013
-
Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 117:33, s. 17078-17083
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Tidskriftsartikel (refereegranskat)abstract
- We show that the formation of the wetting layer and the experimentally observed continuous shift of the H2O-OH balance toward molecular water at increasing coverage on a TiO2(110) surface can be rationalized on a molecular level. The mechanism is based on the initial formation of stable hydroxyl pairs, a repulsive interaction between these pairs, and an attractive interaction with respect to water molecules. The experimental data are obtained by synchrotron radiation photoelectron spectroscopy and interpreted with the aid of density functional theory calculations and Monte Carlo simulations.
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| 25. |
- Amidani, Lucia, et al.
(författare)
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Oxygen K-Edge X-ray Absorption Spectra of ThO2 and CeO2 : Experiment, Interpretation, and Structural Effects
- 2023
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 127:6, s. 3077-3084
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Tidskriftsartikel (refereegranskat)abstract
- Experimental oxygen K-edge spectra of ThO2 and CeO2 are presented and interpreted based on density functional theory (DFT). The contribution of d and f orbitals to the O Kedge spectrum is identified as well-distinguished peaks, the presence of which evidences the strong hybridization of Th and Ce metal centers with O orbitals. The sensitivity of the O K-edge to both f- and d-states in the absence of a core-hole on the metal ion results in an insightful overview of the electronic structure involved in the chemical bond. In particular, the large bandwidth of the Th 5f band as compared to the Ce 4f band is observed as a set of wider and more substantial set of peaks in the O K-edge, confirming the stronger hybridization of the former with O orbitals. The peak ascribed to the 5f band of ThO2 is found at higher energy than the 6d band, as predicted from DFT calculations on actinide dioxides. To highlight the sensitivity and the potential use of the O K-edge for the characterization of ThO2-based systems, the sensitivity of the spectrum to structural changes such as lattice expansion and size reduction are calculated and discussed.
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