Lateral Hopping of CO on Ag(110) by Multiple Overtone Excitation

A novel type of action spectrum representing multiple overtone excitations of the upsilon(M-C) mode was observed for lateral hopping of a CO molecule on Ag(110) induced by inelastically tunneled electrons from the tip of a scanning tunneling microscope. The yield of CO hopping shows sharp increases at 261 +/- 4 mV, corresponding to the C-O internal stretching mode, and at 61 +/- 2, 90 +/- 2, and 148 +/- 7 mV, even in the absence of corresponding fundamental vibrational modes. The mechanism of lateral CO hopping on Ag (110) was explained by the multistep excitation of overtone modes of upsilon(M-C) based on the numerical fitting of the action spectra, the nonlinear dependence of the hopping rate on the tunneling current, and the hopping barrier obtained from thermal diffusion experiments.ope

Identification of an AgS2 Complex on Ag(110)

Adsorbed sulfur has been investigated on the Ag(110) surface at two different coverages, 0.02 and 0.25 monolayers. At the lower coverage, only sulfur adatoms are present. At the higher coverage, there are additional bright features which we identify as linear, independent AgS2 complexes. This identification is based upon density functional theory (DFT) and its comparison with experimental observations including bias dependence and separation between complexes. DFT also predicts the absence of AgS2 complexes at low coverage, and the development of AgS2 complexes around a coverage of 0.25 monolayers of sulfur, as is experimentally observed. To our knowledge, this is the first example of an isolated linear sulfur-metal-sulfur complex

Search for the Structure of a Sulfur-Induced Reconstruction on Cu(111)

We have carried out an extensive DFT-based search for the structure of the (√43 × √43)R ± 7.5° reconstruction of S on Cu(111), which exhibits a honeycombtype structure in scanning tunneling microscopy (STM). We apply two criteria in this search: The structure must have a reasonably low chemical potential, and it must provide a good match with STM data, both our own and the data published by Wahlström et al. Phys. Rev. B 1999, 60, 10699. The best model has 12 S adatoms and 9 Cu adatoms per unit cell. Local defects within the Cu9S12 framework, consisting of one missing or one extra Cu adatom per unit cell, would be difficult to detect with STM and would not be energetically costly. There is no obvious correlation between this model and the structure of bulk CuS. If the √43 reconstruction is viewed in terms of local building blocks, then CuS3 and CuS2 clusters, linked by shared S atoms, provides the best description

Long-Range Displacive Reconstruction of Au(110) Triggered by Low Coverage of Sulfur

We propose a new model for the c(4 × 2) phase of sulfur adsorbed on Au(110). This is a reconstruction achieved by short-range rearrangements of Au atoms that create a pseudo-4-fold-hollow (p4fh) site for adsorbed sulfur. The model is based partly upon the agreement between experimental STM images and those predicted from DFT, both within c(4 × 2) domains and at a boundary between two domains. It is also based on the stability of this structure in DFT, where it is not only favored over the chemisorbed phase at its ideal coverage of 0.25 ML, but also at lower coverage (at T = 0 K). This is compatible with the fact that in experiments, it coexists with 0.06 ± 0.03 ML of sulfur chemisorbed on the (1 × 2) surface. The relative stability of the c(4 × 2) phase at 0.25 ML has been verified for a variety of functionals in DFT. In the chemisorbed phase, sulfur adsorbs at a pseudo-3-fold-hollow (p3fh) site near the tops of rows in the (1 × 2) reconstruction. This is similar to the fcc site on an extended (111) surface. Sulfur causes a slight separation between the two topmost Au atoms, which is apparent both in STM images and in DFT-optimized structures. The second-most stable site is also a p3fh site, similar to an hcp site. DFT is used to construct a simple lattice gas model based on pairs of excluded sites. The set of excluded sites is in good qualitative agreement with our STM data. From DFT, the diffusion barrier of a sulfur atom is 0.61 eV parallel to the Au row, and 0.78 eV perpendicular to the Au row. For the two components of the perpendicular diffusion path, that is, crossing a trough and hopping over a row, the former is considerably more difficult than the latter

Characteristics of sulfur atoms adsorbed on Ag(100), Ag(110), and Ag(111) as probed with scanning tunneling microscopy: experiment and theory

In this paper, we report that S atoms on Ag(100) and Ag(110) exhibit a distinctive range of appearances in scanning tunneling microscopy (STM) images, depending on the sample bias voltage, VS. Progressing from negative to positive VS, the atomic shape can be described as a round protrusion surrounded by a dark halo (sombrero) in which the central protrusion shrinks, leaving only a round depression. This progression resembles that reported previously for S atoms on Cu(100). We test whether DFT can reproduce these shapes and the transition between them, using a modified version of the Lang–Tersoff–Hamann method to simulate STM images. The sombrero shape is easily reproduced, but the sombrero-depression transition appears only for relatively low tunneling current and correspondingly realistic tip–sample separation, dT, of 0.5–0.8 nm. Achieving these conditions in the calculations requires sufficiently large separation (vacuum) between slabs, together with high energy cutoff, to ensure appropriate exponential decay of electron density into vacuum. From DFT, we also predict that an analogous transition is not expected for S atoms on Ag(111) surfaces. The results are explained in terms of the through-surface conductance, which defines the background level in STM, and through-adsorbate conductance, which defines the apparent height at the point directly above the adsorbate. With increasing VS, for Ag(100) and Ag(110), we show that through-surface conductance increases much more rapidly than through-adsorbate conductance, so the apparent adsorbate height drops below background. In contrast, for Ag(111) the two contributions increase at more comparable rates, so the adsorbate level always remains above background and no transition is seen

Support effect of anode catalysts using an organic metal complex for fuel cells

The carbon support effect of Pt–Ni(mqph) electrocatalysts on the performance of CO tolerant anode catalysts for polymer electrolyte fuel cells (PEFCs) was investigated using carbon black and multi-walled carbon nanotubes (MWCNTs), with and without defect preparation. 20%Pt–Ni(mqph)/defect-free CNTs showed a very high CO tolerance (75% compared to the CO-free H2 case) under 100 ppm CO level in the half-cell system of the hydrogen oxidation reaction. On the other hand, the hydrogen oxidation current on Pt–Ni(mqph)/defective CNTs, Pt–Ni(mqph)/VulcanXC-72R and Pt–Ru/VulcanXC-72R significantly decreased with increasing concentration of CO up to 100 ppm (25–47% compared to the CO-free H2 case). It is thus considered that the carbon support materials strongly affect the CO tolerance of anode catalysts. This is ascribed to a change in the electronic structure of the Pt particles due to the interaction with the graphene surface, leading to a reduction in the adsorption energy of CO. Ni(mqph) also mitigates CO poisoning due to its ability of CO coordination on Ni metal center

Cu2 S3 complex on Cu(111) as a candidate for mass transport enhancement

Sulfur-metal complexes, containing only a few atoms, can open new, highly efficient pathways for transport of metal atoms on surfaces. For example, they can accelerate changes in the shape and size of morphological features, such as two-dimensional nanoclusters, over time. In this study we perform STM under conditions that are designed to specifically isolate such complexes. We find a new, unexpected S-Cu complex on the Cu(111) surface, which we identify as Cu2S3. We propose that Cu2S3 enhances mass transport in this system, which contradicts a previous proposal based on Cu3S3. We analyze bonding within these Cu-S complexes, identifying a principle for stabilization of sulfur complexes on coinage metal surfaces.open44

Search for the Structure of a Sulfur-Induced Reconstruction on Cu(111)

We have carried out an extensive DFT-based search for the structure of the (√43 × √43)R ± 7.5° reconstruction of S on Cu(111), which exhibits a honeycombtype structure in scanning tunneling microscopy (STM). We apply two criteria in this search: The structure must have a reasonably low chemical potential, and it must provide a good match with STM data, both our own and the data published by Wahlström et al. Phys. Rev. B 1999, 60, 10699. The best model has 12 S adatoms and 9 Cu adatoms per unit cell. Local defects within the Cu9S12 framework, consisting of one missing or one extra Cu adatom per unit cell, would be difficult to detect with STM and would not be energetically costly. There is no obvious correlation between this model and the structure of bulk CuS. If the √43 reconstruction is viewed in terms of local building blocks, then CuS3 and CuS2 clusters, linked by shared S atoms, provides the best description.Reprinted (adapted) with permission from Journal of Physical Chemistry C 118 (2014): 29218, doi: 10.1021/jp505351g. Copyright 2014 American Chemical Society.</p