Refine
Year of publication
Document Type
- Article (20)
Language
- English (20)
Has Fulltext
- yes (20)
Is part of the Bibliography
- no (20) (remove)
Keywords
- Adsorption (6)
- Dichtefunktionalformalismus (5)
- Graphen (4)
- Wasserstoff (3)
- density functional theory (3)
- Bildgebendes Verfahren (2)
- Diffusion (2)
- Eisen <gamma-> (2)
- Flugzeitspektrometrie (2)
- Funktionalisierung <Chemie> (2)
- Gas-Flüssigkeit-System (2)
- Laserphotolyse (2)
- Photodesorption (2)
- Spektroskopie (2)
- Squalan (2)
- Wasserstoffversprödung (2)
- gamma iron (2)
- surface relaxation (2)
- ASW (1)
- Amorphes Eis (1)
- Atomic force microscopy (1)
- Bilderzeugung (1)
- CVD-Verfahren (1)
- Catalysts and Catalysis (1)
- Chemical properties (1)
- Chloroform (1)
- Collisions (1)
- Density functional theory (1)
- Dodekan (1)
- Elektronenbestrahlung (1)
- Energy (1)
- Exciton Migration (1)
- Ferrite (1)
- Ferritic steels (1)
- Ferritischer Stahl (1)
- Flüssigkeitsstrahl (1)
- Graphene (1)
- Haber-Bosch-Verfahren (1)
- Haber–Bosch process (1)
- Hydrierung (1)
- Hydrogen Evolution (1)
- Hydrogen embrittlement (1)
- Hydrogenation process (1)
- Hydroxide (1)
- Hydroxyl (1)
- Kaliumbromid (1)
- Kohlenwasserstoffe (1)
- Magnetismus (1)
- Molecules (1)
- Molekulardynamik (1)
- Monoschicht (1)
- Nanoparticles (1)
- Nanopartikel (1)
- Nichtlineare Spektroskopie (1)
- Nichtlinerae Spektroskopie (1)
- Oberflächentemperatur (1)
- Phenylgruppe (1)
- Photodissoziation (1)
- Plasma processing (1)
- Radiolyse (1)
- Radiolysis (1)
- Raman spectroscopy (1)
- Reaktionsdynamik (1)
- Reaktivität (1)
- Sauerstoff (1)
- Sauerstoffatom (1)
- Scattering (1)
- Semiconductors (1)
- Stahl (1)
- Stickstoffmonoxid (1)
- Summenfrequenzerzeugung (1)
- Transition metal chalcogenides (1)
- Two dimensional materials (1)
- VSFS (1)
- Van der Waals forces (1)
- Van-der-Waals-Kraft (1)
- Verdampfung (1)
- Versprödung (1)
- Wasserstoffmolekül (1)
- Zirconia (1)
- Zirkoniumverbindungen (1)
- ZrO2 (1)
- amorphous solid water (1)
- chemisorption (1)
- dodecane (1)
- electron irradiation (1)
- evaporation (1)
- ferrite (1)
- hydrogen (1)
- hydrogen diffusion (1)
- hydrogen embrittlement (1)
- liquid jet (1)
- magnetism (1)
- molecular dynamics (1)
- molecurlar hydrogen (1)
- oxidation (1)
- partial density of states (1)
- potential energy surface (1)
- vibrational sum-frequency spectroscopy (1)
Institute
We report velocity-dependent internal energy distributions of nitric oxide molecules, NO, scattered off graphene supported on gold to further explore the dynamics of the collision process between NO radicals and graphene. These experiments were performed by directing a molecular beam of NO onto graphene in a surface-velocity map imaging setup, which allowed us to record internal energy distributions of the NO radicals as a function of their velocity. We do not observe bond formation but (1) major contributions from direct inelastic scattering and (2) a smaller trapping–desorption component where some physisorbed NO molecules have residence times on the order of microseconds. This is in agreement with our classical molecular dynamics simulations which also observe a small proportion of two- and multi-bounce collisions events but likewise a small proportion of NO radicals trapped at the surface for the entire length of the molecular dynamics simulations (a few picoseconds). Despite a collision energy of 0.31 eV, which would be sufficient to populate NO(v = 1), we do not detect vibrationally excited nitric oxide.
In this study, we calculated the energetics of hydrogen atoms adsorbing on and diffusing into the first few layers of γ-Fe for the (100), (110) and (111) surfaces and for the non-magnetic (NM), ferromagnetic (FM), and antiferromagnetic single (AFM1) and double layer (AFMD) structures. These studies are relevant as they atomistically simulate the early stages of hydrogen embrittlement in steels. We employed density functional theory to establish adsorption sites and energies for each plane and the minimum energy pathways for diffusion through the first few layers with associated activation barriers. Adsorption energies for all cases vary between ∼3.7 and 4.4 eV, and the energy barriers to diffusion in the bulk region vary between ∼0.2 and 1.2 eV for the twelve cases, with the highest and lowest bulk diffusion barriers occurring in the NM(111) and the FM(100) case, respectively. We conclude that the texturing of steels in order to expose certain cleavage planes or magnetic structures can decrease the likelihood of hydrogen embrittlement.
A novel method has been implemented to prepare metal oxide nanopowders covered with known quantities of adsorbed water; we subsequently studied the γ-radiolysis of ZrO2 nanopowders covered with H2O layers. H2 yields from the adsorbed water radiolysis are of importance in multiple industrial contexts – the nuclear industry being a prime example. Measured H2 yields at water coverages of just below and above one monolayer are around 350 times greater than for neat water, but these yields decrease rapidly with increasing water loading of the ZrO2 nanoparticles, approaching the yield of bulk water at coverages of tens of water layers. The observed plateau of the yields at 0.5 to 2.0 monolayers coverage can be explained by the ease with which electronic excitations in the ZrO2 can be transferred across the interface to the first one or two adsorbed water layers. However, with increasing water loading, energy transfer to water layers further away from the interface becomes less efficient, and above ~30 water layers, most of the water is not affected by any exciton formation in the ZrO2.
The reactivity of graphene at its boundary region has been imaged using non-linear spectroscopy to address the controversy whether the terraces of graphene or its edges are more reactive. Graphene was functionalised with phenyl groups, and we subsequently scanned our vibrational sum-frequency generation setup from the functionalised graphene terraces across the edges. A greater phenyl signal is clearly observed at the edges, showing evidence of increased reactivity in the boundary region. We estimate an upper limit of 1 mm for the width of the CVD graphene boundary region.
Nitric oxide adsorption on a Au(100) single crystal has been investigated to identify the type of adsorption, the adsorption site, and the orientation and alignment of the adsorbed NO relative to the surface. This was done using a combination of 3D-surface velocity map imaging, near-ambient pressure X-ray photoelectron spectroscopy, and density functional theory. NO was observed to be molecularly adsorbed on gold at ~200 K. Very narrow angular distributions and cold rotational distributions of photodesorbed NO indicate that NO adsorbs on high-symmetry sites on the Au crystal, with the N–O bond axis close to the surface normal. Our density functional theory calculations show that NO preferentially adsorbs on the symmetric bridge (2f) site, which ensures efficient overlap of the NO π* orbital with the orbitals on the two neighbouring Au atoms, and with the N–O bond axis aligned along the surface normal, in agreement with our conclusions from the rotational state distributions. The combination of XPS, which reveals the orientation of NO on gold, with 3D-surface velocity map imaging and density functional theory thus allowed us to determine the adsorption site, orientation and alignment of nitric oxide adsorbed on Au(100).
This study is concerned with the early stages of hydrogen embrittlement on an atomistic scale. We employed density functional theory to investigate hydrogen diffusion through the (100), (110) and (111) surfaces of γ-Fe. The preferred adsorption sites and respective energies for hydrogen adsorption were established for each plane, as well as a minimum energy pathway for diffusion. The H atoms adsorb on the (100), (110) and (111) surfaces with energies of ∼4.06 eV, ∼3.92 eV and ∼4.05 eV, respectively. The barriers for bulk-like diffusion for the (100), (110) and (111) surfaces are ∼0.6 eV, ∼0.5 eV and ∼0.7 eV, respectively. We compared these calculated barriers with previously obtained experimental data in an Arrhenius plot, which indicates good agreement between experimentally measured and theoretically predicted activation energies. Texturing austenitic steels such that the (111) surfaces of grains are preferentially exposed at the cleavage planes may be a possibility to reduce hydrogen embrittlement.
The effect of magnetism on hydrogen adsorption and subsurface diffusion through face-centred cubic (fcc) γ-Fe(0 0 1) was investigated using spin-polarised density functional theory (s-DFT). The non-magnetic (NM), ferromagnetic (FM), and antiferromagnetic single (AFM1) and double layer (AFMD) structures were considered. For each magnetic state, the hydrogen preferentially adsorbs at the fourfold site, with adsorption energies of 4.07, 4.12, 4.03 and 4.05 eV/H atom for the NM, FM, AFM1 and AFMD structures. A total barrier of 1.34, 0.90, 1.32 and 1.25 eV and a bulk-like diffusion barrier of 0.6, 0.2, 0.4 and 0.3 eV were calculated for the NM, FM, AFM1 and AFMD magnetic states. The Fe atoms nearest to the H atom exhibited a reduced magnetic moment, whereas the next-nearest neighbour Fe atoms exhibited a non-negligible local perturbation in the magnetic moment. The presence of magnetically ordered structures has a minimal influence on the minimum energy path for H diffusion through the lattice and on the adsorption of H atoms on the Fe(0 0 1) surface, but we computed a significant reduction of the bulk-like diffusion barriers with respect to the non-magnetic state of fcc γ-Fe.
We report the unambiguous detection of phenyl groups covalently attached to functionalised graphene using non-linear spectroscopy. Sum-frequency generation was employed to probe graphene on a gold surface after chemical functionalisation using a benzene diazonium salt. We observe a distinct resonance at 3064 cm1 which can clearly be assigned to an aromatic C–H stretch by comparison with a self-assembled monolayer on a gold substrate formed from benzenethiol. Not only does sum-frequency generation spectroscopy allow one to characterise functionalised graphene with higher sensitivity and much better specificity than many other spectroscopic techniques, but it also opens up the possibility to assess the coverage of graphene with functional groups, and to determine their orientation relative to the graphene surface.
The adsorption of O atoms on the Fe(1 1 0) surface has been investigated by density functional theory for increasing degrees of oxygen coverage from 0.25 to 1 monolayer, to follow the evolution of the Osingle bondFe(1 1 0) system into an FeO(1 1 1)-like monolayer. We found that the quasi-threefold site is the most stable adsorption site for all coverages, with adsorption energies of ∼2.8–4.0 eV per O atom. Oxygen adsorption results in surface geometrical changes such as interlayer relaxation and buckling, the latter of which decreases with coverage. The calculated vibrational frequencies range from 265 to 470 cm−1 for the frustrated translational modes and 480–620 cm−1 for the stretching mode, and hence are in good agreement with the experimental values reported for bulk FeO wüstite. The hybridization of the oxygen 2p and iron 3d orbitals increases with oxygen coverage, and the partial density of states for the Osingle bondFe(1 1 0) system at full coverage resembles the one reported in the literature for bulk FeO. These results at full oxygen coverage point to the incipient formation of an FeO(1 1 1)-like monolayer that would eventually lead to the bulk FeO oxide layer.
Molecular hydrogen production from amorphous solid water during low energy electron irradiation
(2017)
This work investigates the production of molecular hydrogen isotopologues (H2, HD, and D2) during low energy electron irradiation of layered and isotopically labelled thin films of amorphous solid water (ASW) in ultrahigh vacuum. Experimentally, the production of these molecules with both irradiation time and incident electron energy in the range 400 to 500 eV is reported as a function of the depth of a buried D2O layer in an H2O film. H2 is produced consistently in all measurements, reflecting the H2O component of the film, though it does exhibit a modest reduction in intensity at the time corresponding to product escape from the buried D2O layer. In contrast, HD and D2 production exhibit peaks at times corresponding to product escape from the buried D2O layer in the composite film. These features broaden the deeper the HD or D2 is formed due to diffusion. A simple random-walk model is presented that can qualitatively explain the appearance profile of these peaks as a function of the incident electron penetration.
The use of vibrational sum-frequency spectroscopy (VSFS) to study transferred graphene, produced by chemical vapour deposition, is presented. The VSF spectrum shows a clear CeH stretching mode at ~2924 cm⁻¹, which is attributed to residue of the polymer used for the transfer. This makes VSFS a powerful tool to identify adsorbates and contaminants affecting the properties of graphene.
The ability to functionalize graphene with several methods, such as radical reactions, cycloadditions, hydrogenation, and oxidations, allows this material to be used in a large range of applications. In this framework, it is essential to be able to control the efficiency and stability of the functionalization process—this requires understanding how the graphene reactivity is affected by the environment, including the substrate. In this work we provide an insight on the substrate dependence of graphene reactivity towards hydrogenation by comparing three different substrates: silicon, hexagonal boron nitride (h-BN), and molybdenum disulfide (MoS2). Although MoS2 and h-BN have flatter surfaces than silicon, we found that the H coverage of graphene on h-BN is about half of the H coverage on graphene on both silicon and MoS2. Therefore, graphene shows strongly reduced reactivity towards hydrogenation when placed on h-BN. The difference in hydrogenation reactivity between h-BN and MoS2 may indicate a stronger van der Waals force between graphene and h-BN, compared to MoS2, or may be related to the chemical properties of MoS2, which is a well-known catalyst for hydrogen evolution reactions.
Surface atomic relaxation and magnetism on hydrogen-adsorbed Fe(110) surfaces from first principles
(2016)
We have computed adsorption energies, vibrational frequencies, surface relaxation and buckling for hydrogen adsorbed on a body-centred-cubic Fe(110) surface as a function of the degree of H coverage. This adsorption system is important in a variety of technological processes such as the hydrogen embrittlement in ferritic steels, which motivated this work, and the Haber–Bosch process. We employed spin-polarised density functional theory to optimise geometries of a six-layer Fe slab, followed by frozen mode finite displacement phonon calculations to compute Fe–H vibrational frequencies. We have found that the quasi-threefold (3f) site is the most stable adsorption site, with adsorption energies of ∼3.0 eV/H for all coverages studied. The long-bridge (lb) site, which is close in energy to the 3f site, is actually a transition state leading to the stable 3f site. The calculated harmonic vibrational frequencies collectively span from 730 to 1220 cm−1, for a range of coverages. The increased first-to-second layer spacing in the presence of adsorbed hydrogen, and the pronounced buckling observed in the Fe surface layer, may facilitate the diffusion of hydrogen atoms into the bulk, and therefore impact the early stages of hydrogen embrittlement in steels.
The velocity distribution of He atoms evaporating from a slab of liquid dodecane has been simulated. The distribution composed of ∼10 000 He trajectories is shifted to fractionally faster velocities as compared to a Maxwell–Boltzmann distribution at the temperature of the liquid dodecane with an average translational energy of 1.05 × 2RT (or 1.08 × 2RT after correction for a cylindrical liquid jet), compared to the experimental work by Nathanson and co-workers (1.14 × 2RT) on liquid jets. Analysis of the trajectories allows us to infer mechanistic information about the modes of evaporation, and their contribution to the overall velocity distribution.
Energy- and angle-resolved photofragment distributions for ground-state Cl (²P₃/₂) and spin–orbit excited Cl* (²P₁/₂) have been recorded using the velocity map imaging technique after photodissociation of chloroform at wavelengths of 193 and ∼235 nm. Translational energy distributions are rather broad and peak between 0.6 and 1.0 eV. The spin–orbit branching ratios [Cl*]/[Cl] are 1 and 0.3 at 193 and 235 nm, respectively, indicating the involvement of two or more excited state surfaces. Considering the anisotropy parameters and branching ratios collectively, we conclude that the reaction at 193 nm takes place predominantly on the ¹Q₁ surface, while the ³Q₁ surface gains importance at lower dissociation energies around 235 nm.
The authors describe the application of a combination of velocity map imaging and time-of-flight (TOF) techniques to obtain three-dimensional velocity distributions for surface photodesorption. They have established a systematic alignment procedure to achieve correct and reproducible experimental conditions. It includes four steps: (1) optimization of the velocity map imaging ion optics’ voltages to achieve optimum velocity map imaging conditions; (2) alignment of the surface normal with the symmetry axis (ion flight axis) of the ion optics; (3) determination of TOF distance between the surface and the ionizing laser beam; (4) alignment of the position of the ionizing laser beam with respect to the ion optics. They applied this set of alignment procedures and then measured Br(²P₃/₂) (Br) and Br(²P₁/₂) (Br∗) atoms photodesorbing from a single crystal of KBr after exposure to 193 nm light. They analyzed the velocity flux and energy flux distributions for motion normal to the surface. The Br∗ normal energy distribution shows two clearly resolved peaks at approximately 0.017 and 0.39 eV, respectively. The former is slightly faster than expected for thermal desorption at the surface temperature and the latter is hyperthermal. The Br normal energy distribution shows a single broad peak that is likely composed of two hyperthermal components. The capability that surface three-dimensional velocity map imaging provides for measuring state-specific velocity distributions in all three dimensions separately and simultaneously for the products of surface photodesorption or surface reactions holds great promise to contribute to our understanding of these processes.
We have combined the velocity map imaging technique with time-of-flight measurements to study the surface photochemistry of KBr single crystals. This approach yields 3-dimensional velocity distributions of Br atoms resulting from 193 nm photodesorption. The velocity distributions indicate that at least two non-thermal mechanisms contribute to the photodesorption dynamics. Our experimental geometry also allows us to measure the Br(²P₃⁄₂):Br(²P₁⁄₂) branching ratio, which is found to be 24:1.
Recent progress that has been made towards understanding the dynamics of collisions at the gas–liquid interface is summarized briefly. We describe in this context a promising new approach to the experimental study of gas–liquid interfacial reactions that we have introduced. This is based on laser-photolytic production of reactive gas-phase atoms above the liquid surface and laser-spectroscopic probing of the resulting nascent products. This technique is illustrated for reaction of O(³P) atoms at the surface of the long-chain liquid hydrocarbon squalane (2,6,10,15,19,23-hexamethyltetracosane). Laser-induced fluorescence detection of the nascent OH has revealed mechanistically diagnostic correlations between its internal and translational energy distributions. Vibrationally excited OH molecules are able to escape the surface. At least two contributions to the product rotational distributions are identified, confirming and extending previous hypotheses of the participation of both direct and trapping-desorption mechanisms. We speculate briefly on future experimental and theoretical developments that might be necessary to address the many currently unanswered mechanistic questions for this, and other, classes of gas–liquid interfacial reaction.
The effects of surface temperature on the gas-liquid interfacial reaction dynamics of O(³P)+squalane
(2005)
OH/OD product state distributions arising from the reaction of gas-phase O(³P) atoms at the surface of the liquid hydrocarbon squalane C₃₀H₆₂/C₃₀D₆₂ have been measured. The O(³P) atoms were generated by 355 nm laser photolysis of NO₂ at a low pressure above the continually refreshed liquid. It has been shown unambiguously that the hydroxyl radicals detected by laser-induced fluorescence originate from the squalane surface. The gas-phase OH/OD rotational populations are found to be partially sensitive to the liquid temperature, but do not adapt to it completely. In addition, rotational temperatures for OH/OD(v′=1) are consistently colder (by 34±5 K) than those for OH/OD(v′=0). This is reminiscent of, but less pronounced than, a similar effect in the well-studied homogeneous gas-phase reaction of O(³P) with smaller hydrocarbons. We conclude that the rotational distributions are composed of two different components. One originates from a direct abstraction mechanism with product characteristics similar to those in the gas phase. The other is a trapping-desorption process yielding a thermal, Boltzmann-like distribution close to the surface temperature. This conclusion is consistent with that reached previously from independent measurements of OH product velocity distributions in complementary molecular-beam scattering experiments. It is further supported by the temporal profiles of OH/OD laser-induced fluorescence signals as a function of distance from the surface observed in the current experiments. The vibrational branching ratios for (v′=1)/(v′=0) for OH and OD have been found to be (0.07±0.02) and (0.30±0.10), respectively. The detection of vibrationally excited hydroxyl radicals suggests that secondary and/or tertiary hydrogen atoms may be accessible to the attacking oxygen atoms.
We describe an experimental approach to the determination of the nascent internal state distribution of gas-phase products of a gas–liquid interfacial reaction. The system chosen for study is O(³P) atoms with the surface of liquid deuterated squalane, a partially branched long-chain saturated hydrocarbon, C₃₀D₆₂. The nascent OD products are detected by laser-induced fluorescence. Both OD (v′=0) and (v′=1) were observed in significant yield. The rotational distributions in both vibrational levels are essentially the same, and are characteristic of a Boltzmann distribution at a temperature close to that of the liquid surface. This contrasts with the distributions in the corresponding homogeneous gas-phase reactions. We propose a preliminary interpretation in terms of a dominant trapping-desorption mechanism, in which the OD molecules are retained at the surface sufficiently long to cause rotational equilibration but not complete vibrational relaxation. The significant yield of vibrationally excited OD also suggests that the surface is not composed entirely of –CD₃ endgroups, but that secondary and/or tertiary units along the backbone are exposed.