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Sample records for au111 electrode surfaces

  1. Electrochemistry of single metalloprotein and DNA-based molecules at Au(111) electrode surfaces.

    PubMed

    Salvatore, Princia; Zeng, Dongdong; Karlsen, Kasper K; Chi, Qijin; Wengel, Jesper; Ulstrup, Jens

    2013-07-22

    We have briefly overviewed recent efforts in the electrochemistry of single transition metal complex, redox metalloprotein, and redox-marked oligonucleotide (ON) molecules. We have particularly studied self-assembled molecular monolayers (SAMs) of several 5'-C6-SH single- (ss) and double-strand (ds) ONs immobilized on Au(111) electrode surfaces via Au-S bond formation, using a combination of nucleic acid chemistry, electrochemistry and electrochemically controlled scanning tunnelling microscopy (in situ STM). Ds ONs stabilized by multiply charged cations and locked nucleic acid (LNA) monomers have been primary targets, with a view on stabilizing the ds-ONs and improving voltammetric signals of intercalating electrochemical redox probes. Voltammetric signals of the intercalator anthraquinone monosulfonate (AQMS) at ds-DNA/Au(111) surfaces diluted by mercaptohexanol are significantly sharpened and more robust in the presence than in the absence of [Co(NH3)6](3+). AQMS also displays robust Faradaic voltammetric signals specific to the ds form on binding to similar LNA/Au(111) surfaces, but this signal only evolves after successive voltammetric scanning into negative potential ranges. Triply charged spermidine (Spd) invokes itself a strong voltammetric signal, which is specific to the ds form and fully matched sequences. This signal is of non-Faradaic, capacitive origin but appears in the same potential range as the Faradaic AQMS signal. In situ STM shows that molecular scale structures of the size of Spd-stabilized ds-ONs are densely packed over the Au(111) surface in potential ranges around the capacitive peak potential.

  2. Shell-isolated nanoparticle-enhanced Raman spectroscopy study of the adsorption behaviour of DNA bases on Au(111) electrode surfaces.

    PubMed

    Wen, Bao-Ying; Jin, Xi; Li, Yue; Wang, Ya-Hao; Li, Chao-Yu; Liang, Miao-Miao; Panneerselvam, Rajapandiyan; Xu, Qing-Chi; Wu, De-Yin; Yang, Zhi-Lin; Li, Jian-Feng; Tian, Zhong-Qun

    2016-06-21

    For the first time, we used the electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) technique to in situ characterize the adsorption behaviour of four DNA bases (adenine, guanine, thymine, and cytosine) on atomically flat Au(111) electrode surfaces. The spectroscopic results of the various molecules reveal similar features, such as the adsorption-induced reconstruction of the Au(111) surface and the drastic Raman intensity reduction of the ring breathing modes after the lifting reconstruction. As a preliminary study of the photo-induced charge transfer (PICT) mechanism, the in situ spectroscopic results obtained on single crystal surfaces are excellently illustrated with electrochemical data.

  3. A study of the influence of halide adsorption on a reconstructed Au(111) electrode by second harmonic generation

    NASA Astrophysics Data System (ADS)

    Friedrich, A.; Shannon, C.; Pettinger, B.

    1991-07-01

    Optical second harmonic generation (SHG) rotational anisotropy measurements were employed to study the influence of specifically adsorbed anions on the reconstructed Au(111)-(1 × 23) surface. Azimuthal rotation of the gold electrode at different potentials yields for the unreconstructed Au(111)-(1 × 1) surface the well-known three-fold symmetry pattern, while for the reconstructed Au(111)-(1 × 23) an additional one-fold symmetry pattern is observed, which leads to an assignment of Cs-symmetry for this surface. Due to the observation of this symmetry change Cs → C3v it is possible to monitor in situ the reversible transition between Au(111)-(1 × 23) and Au(111)-(1 × 1). While in perclorate solution the phase transition occurs over a wide potential region, in halide containing solution the same phase transition is restricted to the sharp potential region typical for the halide adsorption.

  4. Self-assembly of alkanols on Au(111) surfaces.

    PubMed

    Zhang, Hai-Ming; Yan, Jia-Wei; Xie, Zhao-Xiong; Mao, Bing-Wei; Xu, Xin

    2006-05-15

    Self-assembled monolayers (SAMs) of alkanols (1-C(N)H(2N+1)OH) with varying carbon-chain lengths (N = 10-30) have been systematically studied by means of scanning tunneling microscopy (STM) at the interfaces between alkanol solutions (or liquids) and Au(111) surfaces. The carbon skeletons were found to lie flat on the surfaces. This orientation is consistent with SAMs of alkanols on highly oriented pyrolytic graphite (HOPG) and MoS2 surfaces, and also with alkanes on reconstructed Au(111) surfaces. This result differs from a prior report, which claimed that 1-decanol molecules (N = 10) stood on their ends with the OH polar groups facing the gold substrate. Compared to alkanes, the replacement of one terminal CH3 group with an OH group introduces new bonding features for alkanols owing to the feasibility of forming hydrogen bonds. While SAMs of long-chain alkanols (N > 18) resemble those of alkanes, in which the aliphatic chains make a greater contribution, hydrogen bonding plays a more important role in the formation of SAMs of short-chain alkanols. Thus, in addition to the titled lamellar structure, a herringbone-like structure, seldom seen in SAMs of alkanes, is dominant in alkanol SAMs for values of N < 18. The odd-even effect present in alkane SAMs is also present in alkanol SAMs. Thus, the odd N alkanols (alkanols with an odd number of carbon atoms) adopt perpendicular lamellar structures owing to the favorable interactions of the CH3 terminal groups, similar to the result observed for odd alkanes. In contrast to alkanes on Au(111) surfaces, for which no SAMs on an unreconstructed gold substrate were observed, alkanols are capable of forming SAMs on either the reconstructed or the unreconstructed gold surfaces. Structural models for the packing of alkanol molecules on Au(111) surfaces have been proposed, which successfully explain these experimental observations.

  5. A noval in situ study of adsorption processes at Au(111) electrodes by second harmonic generation

    NASA Astrophysics Data System (ADS)

    Pettinger, B.; Lipkowski, J.; Mirwald, S.; Friedrich, A.

    1992-05-01

    Second harmonic generation (SHG) is an in situ spectroscopic tool par excellence for an electrode surface. Since the SHG response is determined by the nonlinear susceptibility tensor of third rank, χ(2), an understanding of the quite complex and different SHG-anisotropy patterns requires the evaluation of the important χijk tensor elements and their distinct dependences on both electrode potential and adsorption of ions or neutral molecules. The Fourier analysis of the azimuthal SHG data reveals that the observed SHG potential dependences arise mainly from two distinct sources: (i) The surface reconstruction, here denoted as Au(111)-(1 × 23) ↔ Au(111)-(1 × 1); it is controlled by potential and ad/desorption of ions or molecules and leads, via the SHG anisotropy, to an observable change in surface symmetry such as C3v ↔ Cs. (ii) The change of charge density of the electrode surface which is caused by potential shifts and/or adsorption processes; it alters mainly the ax term, e.g. the perpendicular part of the nonlinear polarizability of the metal surface.

  6. Self-assembly of flagellin on Au(111) surfaces.

    PubMed

    González Orive, Alejandro; Pissinis, Diego E; Diaz, Carolina; Miñán, Alejandro; Benítez, Guillermo A; Rubert, Aldo; Daza Millone, Antonieta; Rumbo, Martin; Hernández Creus, Alberto; Salvarezza, Roberto C; Schilardi, Patricia L

    2014-11-01

    The adsorption of flagellin monomers from Pseudomonas fluorescens on Au(111) has been studied by Atomic Force Microscopy (AFM), Scanning Tunneling Microscopy (STM), X-ray Photoelectron Spectroscopy (XPS), Surface Plasmon Resonance (SPR), and electrochemical techniques. Results show that flagellin monomers spontaneously self-assemble forming a monolayer thick protein film bounded to the Au surface by the more hydrophobic subunit and exposed to the environment the hydrophilic subunit. The films are conductive and allow allocation of electrochemically active cytochrome C. The self-assembled films could be used as biological platforms to build 3D complex molecular structures on planar metal surfaces and to functionalize metal nanoparticles.

  7. Self-assembly of flagellin on Au(111) surfaces.

    PubMed

    González Orive, Alejandro; Pissinis, Diego E; Diaz, Carolina; Miñán, Alejandro; Benítez, Guillermo A; Rubert, Aldo; Daza Millone, Antonieta; Rumbo, Martin; Hernández Creus, Alberto; Salvarezza, Roberto C; Schilardi, Patricia L

    2014-11-01

    The adsorption of flagellin monomers from Pseudomonas fluorescens on Au(111) has been studied by Atomic Force Microscopy (AFM), Scanning Tunneling Microscopy (STM), X-ray Photoelectron Spectroscopy (XPS), Surface Plasmon Resonance (SPR), and electrochemical techniques. Results show that flagellin monomers spontaneously self-assemble forming a monolayer thick protein film bounded to the Au surface by the more hydrophobic subunit and exposed to the environment the hydrophilic subunit. The films are conductive and allow allocation of electrochemically active cytochrome C. The self-assembled films could be used as biological platforms to build 3D complex molecular structures on planar metal surfaces and to functionalize metal nanoparticles. PMID:25112916

  8. Rotationally inelastic gas--surface scattering: HCl from Au(111)

    SciTech Connect

    Lykke, K.R.; Kay, B.D. )

    1990-02-15

    A quantum-resolved molecular beam--surface scattering study of HCl scattered from Au(111) is described. The HCl is detected in a quantum-resolved manner via (2+1) resonant enhanced multiphoton ionization (REMPI). Greater than 85% of the incident HCl molecules are in a single-quantum state ({ital v}=0, {ital J}=0) with a narrow velocity distribution ({Delta}{upsilon}/{upsilon}{lt}0.10). The scattered HCl is strongly peaked about the specular angle, and both its final velocity and rotational distributions are indicative of direct inelastic scattering. The scattered rotational distributions exhibit features characteristic of rotational rainbows and have a mean rotational energy that displays a bilinear dependence upon the incident normal kinetic energy and surface temperature. The final velocity distributions are largely insensitive to the rotational level and indicate that the energy loss to phonons is small ({lt}20%). Analysis of the scattered data indicates an orientation-averaged attractive well depth of {similar to}5 kcal/mol for the HCl--Au(111) interaction.

  9. Sulfate adsorption at Au(111) electrodes: an optical second harmonic generation study

    NASA Astrophysics Data System (ADS)

    Mirwald, S.; Pettinger, B.; Lipkowski, J.

    1995-07-01

    Second harmonic generation (SHG) generation was employed to study adsorption of sulfate at the Au(111) electrode surface. The experiments were carried out using both pp and ss polarisations for the input and output photons. The amplitudes of the isotropic, one-fold and three-fold symmetry elements of the electrode susceptibility were determined. The isotropic term is a complex number. Its real part displays this same linear dependence on the electrode charge density in the absence and presence of adsorbed sulfate. The phase angle of the complex number is also not changed by sulfate adsorption. These features indicate that adsorbed sulfate changes the static electric field at the interface, however it does not affect the electronic structure of the metal. The one-fold symmetry amplitude changes with potential. This change displays lifting of the surface reconstruction. We observed similar effect of sulfate on the structure of the electrode surface to that reported earlier by Magnussen et al. [Faraday Discuss. 94 (1992) 329].

  10. Scanning Tunneling Microscopy Observations of Benzoic Acid Molecules Coadsorbed with Single-Walled Carbon Nanotubes on Au(111) surface

    NASA Astrophysics Data System (ADS)

    Rabot, Caroline; Clair, Sylvain; Kim, Yousoo; Kawai, Maki

    2007-08-01

    We investigated the interaction of single-walled carbon nanotubes (SWCNTs) with benzoic acid molecules coadsorbed on a Au(111) surface by scanning tunneling microscopy (STM). We studied the self-assembly of the benzoic acid overlayer on Au(111) terraces and along Au(111) step edges and compared the structure of this layer with the benzoic acid molecular structure along SWCNTs.

  11. Electronic modulations in a single wall carbon nanotube induced by the Au(111) surface reconstruction

    SciTech Connect

    Clair, Sylvain; Shin, Hyung-Joon; Kim, Yousoo E-mail: maki@riken.jp; Kawai, Maki E-mail: maki@riken.jp

    2015-02-02

    The structural and electronic structure of single wall carbon nanotubes adsorbed on Au(111) has been investigated by low-temperature scanning tunneling microscopy and spectroscopy. The nanotubes were dry deposited in situ in ultrahigh vacuum onto a perfectly clean substrate. In some cases, the native herringbone reconstruction of the Au(111) surface interacted directly with adsorbed nanotubes and produced long-range periodic oscillations in their local density of states, corresponding to charge transfer modulations along the tube axis. This effect, however, was observed not systematically for all tubes and only for semiconducting tubes.

  12. Adsorption of imidazole on Au(111) surface: Dispersion corrected density functional study

    NASA Astrophysics Data System (ADS)

    Izzaouihda, Safia; Mahjoubi, Khaled; Abou El Makarim, Hassna; Komiha, Najia; Benoit, David M.

    2016-10-01

    We use density functional theory in the generalized gradient approximation to study the adsorption of imidazole on the Au(111) surface and account for dispersion effect using Grimme's empirical dispersion correction technique. Our results show that the adsorption energy of imidazole depends on the slab size and on the adsorption site. In agreement with other studies, we find the largest adsorption energy for imidazole on a top site of Au(111). However, we also note that the adsorption energy at other sites is substantial.

  13. Electronic modulations in a single wall carbon nanotube induced by the Au(111) surface reconstruction

    NASA Astrophysics Data System (ADS)

    Clair, Sylvain; Shin, Hyung-Joon; Kim, Yousoo; Kawai, Maki

    2015-02-01

    The structural and electronic structure of single wall carbon nanotubes adsorbed on Au(111) has been investigated by low-temperature scanning tunneling microscopy and spectroscopy. The nanotubes were dry deposited in situ in ultrahigh vacuum onto a perfectly clean substrate. In some cases, the native herringbone reconstruction of the Au(111) surface interacted directly with adsorbed nanotubes and produced long-range periodic oscillations in their local density of states, corresponding to charge transfer modulations along the tube axis. This effect, however, was observed not systematically for all tubes and only for semiconducting tubes.

  14. Electric field driven changes of a gramicidin containing lipid bilayer supported on a Au(111) surface.

    PubMed

    Laredo, Thamara; Dutcher, John R; Lipkowski, Jacek

    2011-08-16

    Langmuir-Blodgett and Langmuir-Schaeffer methods were employed to deposit a mixed bilayer consisting of 90% of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and 10% of gramicidin (GD), a short 15 residue ion channel forming peptide, onto a Au(111) electrode surface. This architecture allowed us to investigate the effect of the electrostatic potential applied to the electrode on the orientation and conformation of DMPC molecules in the bilayer containing the ion channel. The charge density data were determined from chronocoulometry experiments. The electric field and the potential across the membrane were determined through the use of charge density curves. The magnitudes of potentials across the gold-supported biomimetic membrane were comparable to the transmembrane potential acting on a natural membrane. The information regarding the orientation and conformation of DMPC and GD molecules in the bilayer was obtained from photon polarization modulation infrared reflection absorption spectroscopy (PMIRRAS) measurements. The results show that the bilayer is adsorbed, in direct contact with the metal surface, when the potential across the interface is more positive than -0.4 V and is lifted from the gold surface when the potential across the interface is more negative than -0.4 V. This change in the state of the bilayer has a significant impact on the orientation and conformation of the phospholipid and gramicidin molecules. The potential induced changes in the membrane containing peptide were compared to the changes in the structure of the pure DMPC bilayer determined in earlier studies.

  15. Confining barriers for surface state electrons tailored by monatomic Fe rows on vicinal Au111 surfaces.

    PubMed

    Shiraki, Susumu; Fujisawa, Hideki; Nantoh, Masashi; Kawai, Maki

    2004-03-01

    We fabricated monatomic Fe wires on vicinal Au(111) surfaces and found that decoration of step edges with Fe adatoms has a significant influence on the behavior of surface state electrons confined between regularly arranged steps. On a surface with Fe monatomic rows, angle-resolved photoemission spectra measured in the direction perpendicular to the steps shows parabolic dispersion, in contrast to one-dimensional quantum-well levels observed on a clean surface. Simple analysis using a one-dimensional Kronig-Penney model reveals potential barrier reduction from 20 to 4.6 eV A, suggesting an attractive nature of the Fe adatoms as scatterers.

  16. Structure and Dynamics of the Au(111) Surface in an Electrochemical Enviroment

    NASA Astrophysics Data System (ADS)

    Collini, John; Liu, Yihua; McDonough, Bryanne; Pierce, Michael; You, Hoydoo; Komanicky, Vladimir; Barbour, Andi

    The Au(111) surface possesses a well-known herringbone surface reconstruction pattern. However, the character of the reconstruction's response to external variables is not completely understood due to the limited amount of kinetics and dynamics studies of the surface in different environments. Here, we present in-situ x-ray scattering measurements from the Advanced Photon Source at Argonne National Laboratory of the Au(111) surface in a controllable electrochemical environment of weak NaF solution. Crystal truncation rod (CTR) measurements were taken to examine how the average surface properties and overall structure change with cell voltage. X-ray photon correlation spectroscopy (XPCS) measurements were also taken to examine how the dynamics of the surface change with voltage. The relation between applied potential, average kinetics, and microstate dynamics will be discussed. Funding provided by Research Corporation for Science Advancement. Work done at the Advanced Photon Source supported by the U.S. Department of Energy.

  17. Electron hole pair mediated vibrational excitation in CO scattering from Au(111): Incidence energy and surface temperature dependence

    SciTech Connect

    Shirhatti, Pranav R.; Werdecker, Jörn; Golibrzuch, Kai; Wodtke, Alec M.; Bartels, Christof

    2014-09-28

    We investigated the translational incidence energy (E{sub i}) and surface temperature (T{sub s}) dependence of CO vibrational excitation upon scattering from a clean Au(111) surface. We report absolute v = 0 → 1 excitation probabilities for E{sub i} between 0.16 and 0.84 eV and T{sub s} between 473 and 973 K. This is now only the second collision system where such comprehensive measurements are available – the first is NO on Au(111). For CO on Au(111), vibrational excitation occurs via direct inelastic scattering through electron hole pair mediated energy transfer – it is enhanced by incidence translation and the electronically non-adiabatic coupling is about 5 times weaker than in NO scattering from Au(111). Vibrational excitation via the trapping desorption channel dominates at E{sub i} = 0.16 eV and quickly disappears at higher E{sub i}.

  18. Oxidic copper on the Au(111) surface: A theoretical surface science approach

    NASA Astrophysics Data System (ADS)

    Lee, Taehun; Lee, Yonghyuk; Kang, Kisung; Soon, Aloysius

    Recently, via reactive Cu deposition in an oxygen ambience, high quality gold-supported cuprous oxide (Cu2O) ultrathin nanofilms have been prepared as a model system to further such catalytic studies. Nonetheless, an accurate atomic picture of these ultrathin Cu2O nanofilms, which largely depends on its immediate oxygen environment, is currently lacking. In this work, we perform density-functional theory (DFT) calculations using the Vienna ab initio Simulation Package in combination with ab initio atomistic thermodynamics to investigate stability of Cu2O thin films on Au(111) as a function of oxygen chemical potential. Our results indeed show that some of the surface structures suggested in Ref. are energetically more stable than the traditional copper oxide thin film structures on copper substrate, and elucidated the electronic structure of these ultrathin copper oxide films on gold, in comparison with available experimental data.

  19. Preparation of TiO2 nanocrystallites by oxidation of Ti-Au111 surface alloy.

    PubMed

    Potapenko, Denis V; Osgood, Richard M

    2009-06-01

    Ti-Au surface alloy oxidation is used to form nanocrystals of TiO(2) on Au(111). In situ scanning tunneling microscopy (STM) studies show that the approach yields arrays of 8-11 nm wide crystals with relatively narrow size dispersion and uniform crystallography. STM imaging shows that their crystallographic form is rutile with a triangular or hexagonal geometry. Scanning tunneling spectroscopy indicates that the crystals have a well-developed band gap, comparable to that in bulk TiO(2).

  20. Quantitative Subtractively Normalized Interfacial Fourier Transform Infrared Reflection Spectroscopy Study of the Adsorption of Adenine on Au(111) Electrodes.

    PubMed

    Prieto, Francisco; Su, Zhangfei; Leitch, J Jay; Rueda, Manuela; Lipkowski, Jacek

    2016-04-26

    Quantitative subtractively normalized interfacial Fourier transform infrared reflection spectroscopy (SNIFTIRS) was used to determine the molecular orientation and identify the metal-molecular interactions responsible for the adsorption of adenine from the bulk electrolyte solution onto the surface of the Au(111) electrode. The recorded p-polarized IR spectra of the adsorbed species were subtracted from the collected s-polarized IR spectra to remove the IR contributions of the vibrational bands of the desorbed molecules that are located within the thin layer cavity of the spectroelectrochemical cell. The intense IR band around 1640 cm(-1), which is assigned to the pyrimidine ring stretching vibrations of the C5-C6 and C6-N10 bonds, and the IR band at 1380 cm(-1), which results from a combination of the ring stretching vibration of the C5-C7 bond and the in-plane CH bending vibration, were selected for the quantitative analysis measurements. The transition dipoles of these bands were evaluated by DFT calculations. Their orientations differed by 85 ± 5°. The tilt angles of adsorbed adenine molecules were calculated from the intensity of these two vibrations at different potentials. The results indicate that the molecular plane is tilted at an angle of 40° with respect to the surface normal of the electrode and rotates by 16° around its normal axis with increasing electrode potential. This orientation results from the chemical interaction between the N10 and gold atoms coupled with the π-π parallel stacking interactions between the adjacent adsorbed molecules. Furthermore, the changes in the molecular plane rotation with the electric field suggests that the N1 atom of adenine must also participate in the interaction between the molecule and metal.

  1. Theoretical study of para-nitro-aniline adsorption on the Au(111) surface

    NASA Astrophysics Data System (ADS)

    Li, Cui; Monti, Susanna; Li, Xin; Rinkevicius, Zilvinas; Ågren, Hans; Carravetta, Vincenzo

    2016-07-01

    The electronic structure, bonding properties and dynamics of para-nitro-aniline (PNA) adsorbed on the Au(111) surface for a sub-monolayer coverge have been investigated by density-functional theory (DFT) static calculations and quantum molecular dynamics simulations. Four main adsorption geometries have been identified by DFT energy optimization with the gradient corrected PBE functional and accounting for the role of the van del Waals (vdW) interaction. Quantum dynamics calculations starting from the four different structures have been performed at room temperature to estimate the relative stability of the adsorbates and the presence of barriers for their interconversion. Quantum simulations suggest that the most stable adsorption geometry at room temperature is that of PNA with a slightly distorted molecular plane almost parallel to the Au(111) surface. In a second less populated configuration the PNA molecule interacts with the substrate by its NO2 group while the molecular plane is orthogonal to the surface. The N 1s electron photoemission spectrum has been simulated for the identified adsorbate geometries and a measurable variation of the absolute and relative chemical shift for the two nitrogen atoms in comparison with the known values for PNA in gas phase is predicted.

  2. Enthalpy-Entropy Tuning in the Adsorption of Nucleobases at the Au(111) Surface.

    PubMed

    Rosa, Marta; Corni, Stefano; Di Felice, Rosa

    2014-04-01

    The interaction of DNA molecules with hard substrates is of paramount importance both for the study of DNA itself and for the variety of possible technological applications. Interaction with inorganic surfaces strongly modifies the helical shape of DNA. Hence, an accurate understanding of DNA structure and function at interfaces is a fundamental question with enormous impact in science and society. This work sets the fundamentals for the simulation of entire DNA oligomers on gold surfaces in dry and wet conditions. Thanks to the new GolDNA-AMBER force field, which was derived from first principles and includes dispersion interactions and polarization effects, we simulated self-assembled guanine and adenine monolayers on Au(111) in vacuo and the adsorption of all nucleobases on the same substrate in aqueous conditions. The periodic monolayers obtained from classical simulations match very well those from first principle calculations and experiments, assessing the robustness of the force field and motivating the application to more complex systems for which quantum calculations are not affordable and experiments are elusive. The energetics of nucleobases on Au(111) in solution reveal fundamental physicochemical effects: we find that the adsorption paradigm shifts from purely enthalpic to dominantly entropic by changing the environment and aggregation phase.

  3. Effects of chlorine and oxygen coverage on the structure of the Au(111) surface

    SciTech Connect

    Baker, Thomas A.; Friend, Cynthia M.; Kaxiras, Efthimios

    2009-02-28

    We investigate the effects of Cl and O coverage on the atomic structure of the Au(111) surface using density functional theory calculations. We find that the release and incorporation of gold atoms in the adsorbate layer becomes energetically favorable only at high coverages of either O or Cl (>0.66 ML (monolayer) for O and >0.33 ML for Cl), whereas adsorption without the incorporation of gold is favorable at lower coverages. The bonding between the adsorbate and gold substrate changes significantly with coverage, becoming more covalent (less ionic) at higher Cl and O coverage. This is based on the fact that at higher coverages there is less ionic charge transfer to the adsorbate, while the electron density in the region between the adsorbate and a surface gold atom is increased. Our results illustrate that the O and Cl coverage on Au(111) can dramatically affect its structure and bonding, which are important features in any application of gold involving these adsorbates.

  4. Coverage-dependent Orientations of Dy@C82 Molecules on Au(111) Surface

    NASA Astrophysics Data System (ADS)

    Chen, Feng-yun; Hu, Zhen-peng

    2012-08-01

    The adsorption and molecular orientation of Dy@C82 isomer I on Au(111) has been investigated using ultrahigh-vacuum scanning tunneling microscopy at 80 K. At low coverages, the Dy@C82 molecules tend to grow along the step edges of Au(111), forming small clusters and molecular chains. Adsorption of Dy@C82 on the edges is dominated by the fullerene-substrate interaction and presents various molecular orientations. At higher coverages, the Dy@C82 is found to form ordered islands consisting of small domains of equally oriented molecules. The Dy@C82 molecules in the islands prefer the adsorption configurations with the major C2 axis being approximately parallel to the surface of the substrate. Three preferable orientations of the Dy@C82 molecules are found in a two-dimensional hexagonal close packed overlayer. These observations are attributed to the interplay of the fullerene-substrate interaction and dipole-dipole interaction between the metallofullerenes.

  5. Transition metal dimer on Au(111) surface: A first principle study

    SciTech Connect

    Sahoo, Suman Kalyan; Nigam, Sandeep; Sarkar, Pranab; Majumder, Chiranjib

    2012-06-05

    The adsorption behaviour of transition metal dimers M{sub 2} (M= Cu, Ag, Au) on the Au(111) surface have been studied using the density functional theory formalism. The projector augmented wave method under the spin polarized version of generalized gradient approximation scheme was employed to calculate the total energy. The results suggest that all dimers prefer to orient in parallel to the surface plane, where two M atoms are adsorbed on two nearby threefold fcc sites. We have investigated the chemical interaction between M atoms and Au surface through electronic density of state analysis. It is found that on deposition, the electronic density of states (EDOS) of M{sub 2} dimer becomes broader in comparison to their gas phase spectrum.

  6. Transition metal dimer on Au(111) surface: A first principle study

    NASA Astrophysics Data System (ADS)

    Sahoo, Suman Kalyan; Nigam, Sandeep; Sarkar, Pranab; Majumder, Chiranjib

    2012-06-01

    The adsorption behaviour of transition metal dimers M2 (M= Cu, Ag, Au) on the Au(111) surface have been studied using the density functional theory formalism. The projector augmented wave method under the spin polarized version of generalized gradient approximation scheme was employed to calculate the total energy. The results suggest that all dimers prefer to orient in parallel to the surface plane, where two M atoms are adsorbed on two nearby threefold fcc sites. We have investigated the chemical interaction between M atoms and Au surface through electronic density of state analysis. It is found that on deposition, the electronic density of states (EDOS) of M2 dimer becomes broader in comparison to their gas phase spectrum.

  7. Self-assembly of thiolated cyanine aggregates on Au(111) and Au nanoparticle surfaces

    NASA Astrophysics Data System (ADS)

    Menéndez, Guillermo O.; Cortés, Emiliano; Grumelli, Doris; Méndez de Leo, Lucila P.; Williams, Federico J.; Tognalli, Nicolás G.; Fainstein, Alejandro; Vela, María Elena; Jares-Erijman, Elizabeth A.; Salvarezza, Roberto C.

    2012-01-01

    Heptamethinecyanine J-aggregates display sharp, intense fluorescence emission making them attractive candidates for developing a variety of chem-bio-sensing applications. They have been immobilized on planar thiol-covered Au surfaces and thiol-capped Au nanoparticles by weak molecular interactions. In this work the self-assembly of novel thiolated cyanine (CNN) on Au(111) and citrate-capped AuNPs from solutions containing monomers and J-aggregates has been studied by using STM, XPS, PM-IRRAS, electrochemical techniques and Raman spectroscopy. Data show that CNN species adsorb on the Au surfaces by forming thiolate-Au bonds. We found that the J-aggregates are preferentially adsorbed on the Au(111) surface directly from the solution while adsorbed CNN monomers cannot organize into aggregates on the substrate surface. These results indicate that the CNN-Au interaction is not able to disorganize the large J-aggregates stabilized by π-π stacking to optimize the S-Au binding site but it is strong enough to hinder the π-π stacking when CNNs are chemisorbed as monomers. The optical properties of the J-aggregates remain active after adsorption. The possibility of covalently bonding CNN J-aggregates to Au planar surfaces and Au nanoparticles controlling the J-aggregate/Au distance opens a new path regarding their improved stability and the wide range of biological applications of both CNN and AuNP biocompatible systems.Heptamethinecyanine J-aggregates display sharp, intense fluorescence emission making them attractive candidates for developing a variety of chem-bio-sensing applications. They have been immobilized on planar thiol-covered Au surfaces and thiol-capped Au nanoparticles by weak molecular interactions. In this work the self-assembly of novel thiolated cyanine (CNN) on Au(111) and citrate-capped AuNPs from solutions containing monomers and J-aggregates has been studied by using STM, XPS, PM-IRRAS, electrochemical techniques and Raman spectroscopy. Data show

  8. One-dimensional Fe Nanostructures Formed on Vicinal Au(111) Surfaces

    NASA Astrophysics Data System (ADS)

    Shiraki, Susumu; Fujisawa, Hideki; Nantoh, Masashi; Kawai, Maki

    2005-07-01

    In this study of fabricated one-dimensional (1D) nanostructures of Fe adatoms on vicinal Au(111) surfaces, the growth mechanism and electronic structures are investigated by scanning tunneling microscopy (STM) and by angle-resolved photoemission spectroscopy (ARPES). STM observations reveal that dosed Fe atoms are trapped at the lower corners of the steps. They create nucleation centers near the intersections between steps and discommensuration lines, and grow into evenly spaced Fe fragments located at face-centered-cubic (fcc) stacking regions of the substrate. The connection of these fragments aligned along the steps results in the formation of Fe monatomic rows. As the Fe coverage increases, the Fe growth proceeds predominantly at the fcc stacking regions, and forms quasi-1D nanostructures with undulating edges. At an Fe coverage of ˜0.6 ML, the fast-growing parts connect with the adjacent Fe structures and a two-dimensional network structure is built up. ARPES measurements reveal that the decoration of the step edges with Fe has a significant influence on the periodic potential of the surface state electrons confined between the regularly arranged steps. On the surface with Fe monatomic rows, photoemission spectra measured in the direction perpendicular to the steps show a parabolic dispersion of the Au(111) surface state with downward energy shift of the band bottom; the clean surface, in contrast, shows two 1D quantum-well levels. A simple analysis using a 1D Kronig-Penny model reveals that the Fe decoration reduces the potential barrier height at the steps from 20 to 4.6 eV Å, suggesting that the Fe adatoms work as attractive scatterers and increase the probability of transmission through the barriers. Furthermore, for the higher Fe coverage, the spectra reflecting the electronic nature of the 1D nanostructures show little dispersion, suggesting that the Fe 3d states are localized in the 1D structures.

  9. Adsorption and switching properties of a N-benzylideneaniline based molecular switch on a Au(111) surface

    SciTech Connect

    Ovari, Laszlo; Luo, Ying; Haag, Rainer; Leyssner, Felix; Tegeder, Petra; Wolf, Martin

    2010-07-28

    High resolution electron energy loss spectroscopy has been employed to analyze the adsorption geometry and the photoisomerization ability of the molecular switch carboxy-benzylideneaniline (CBA) adsorbed on Au(111). CBA on Au(111) adopts a planar (trans) configuration in the first monolayer (ML) as well as for higher coverages (up to 6 ML), in contrast to the strongly nonplanar geometry of the molecule in solution. Illumination with UV light of CBA in direct contact with the Au(111) surface ({<=}1 ML) caused no changes in the vibrational structure, whereas at higher coverages (>1 ML) pronounced modifications of vibrational features were observed, which we assign to a trans{yields}cis isomerization. Thermal activation induced the back reaction to trans-CBA. We propose that the photoisomerization is driven by a direct (intramolecular) electronic excitation of the adsorbed CBA molecules in the second ML (and above) analogous to CBA in the liquid phase.

  10. Six-dimensional quantum dynamics study for the dissociative adsorption of HCl on Au(111) surface

    SciTech Connect

    Liu, Tianhui; Fu, Bina; Zhang, Dong H.

    2013-11-14

    The six-dimensional quantum dynamics calculations for the dissociative chemisorption of HCl on Au(111) are carried out using the time-dependent wave-packet approach, based on an accurate PES which was recently developed by neural network fitting to density functional theory energy points. The influence of vibrational excitation and rotational orientation of HCl on the reactivity is investigated by calculating the exact six-dimensional dissociation probabilities, as well as the four-dimensional fixed-site dissociation probabilities. The vibrational excitation of HCl enhances the reactivity and the helicopter orientation yields higher dissociation probability than the cartwheel orientation. A new interesting site-averaged effect is found for the title molecule-surface system that one can essentially reproduce the six-dimensional dissociation probability by averaging the four-dimensional dissociation probabilities over 25 fixed sites.

  11. Six-dimensional quantum dynamics study for the dissociative adsorption of HCl on Au(111) surface.

    PubMed

    Liu, Tianhui; Fu, Bina; Zhang, Dong H

    2013-11-14

    The six-dimensional quantum dynamics calculations for the dissociative chemisorption of HCl on Au(111) are carried out using the time-dependent wave-packet approach, based on an accurate PES which was recently developed by neural network fitting to density functional theory energy points. The influence of vibrational excitation and rotational orientation of HCl on the reactivity is investigated by calculating the exact six-dimensional dissociation probabilities, as well as the four-dimensional fixed-site dissociation probabilities. The vibrational excitation of HCl enhances the reactivity and the helicopter orientation yields higher dissociation probability than the cartwheel orientation. A new interesting site-averaged effect is found for the title molecule-surface system that one can essentially reproduce the six-dimensional dissociation probability by averaging the four-dimensional dissociation probabilities over 25 fixed sites.

  12. Nanostructure of [Li(G4)] TFSI and [Li(G4)] NO3 solvate ionic liquids at HOPG and Au(111) electrode interfaces as a function of potential.

    PubMed

    McLean, Ben; Li, Hua; Stefanovic, Ryan; Wood, Ross J; Webber, Grant B; Ueno, Kazuhide; Watanabe, Masayoshi; Warr, Gregory G; Page, Alister; Atkin, Rob

    2015-01-01

    Atomic force microscopy (AFM) force measurements have been used to study the solvate ionic liquid (IL) double layer nanostructure at highly ordered pyrolytic graphite (HOPG) and Au(111) electrode surfaces as a function of potential. Two solvate ILs are investigated, [Li(G4)] TFSI and [Li(G4)] NO3. Normal force versus apparent separation data indicates that both solvate ILs adopt a multilayered morphology at the electrode interface, similar to conventional ILs. Calculations of adsorption free energies indicate that at 0 V the ion layer in contact with the electrode surface is enriched in the more surface active cations. When a positive or negative surface bias is applied, the concentration of counterions in the innermost layer increases, and higher push-through forces are required to displace near surface layers, indicating a stronger interfacial structure. Generally, [Li(G4)] TFSI has a better defined structure than [Li(G4)] NO3 on both electrode surfaces due to stronger cohesive interactions within layers. Interfacial structure is also better defined for both solvate ILs on HOPG than Au(111) due to the greater surface roughness of Au(111). Further, at all negative potentials on both surfaces, a small final step is observed, consistent with either compression of the complex cation adsorbed structure or desolvation of the glyme from the Li(+).

  13. Spin waves in ultrathin hexagonal cobalt films on W(110), Cu(111), and Au(111) surfaces

    NASA Astrophysics Data System (ADS)

    Michel, E.; Ibach, H.; Schneider, C. M.

    2015-07-01

    Spin wave spectra of ultrathin epitaxial cobalt films deposited on W(110), Cu(111), and Au(111) surfaces are studied in the wave-vector regime between 0.1 Å-1 and 0.7 Å-1 using inelastic electron scattering with 6 meV energy resolution. Up to three different spin wave modes are resolved for wave vectors q∥<0.35 Å-1 . The modes are identified as the acoustic mode and standing modes with one and two nodes inside the film. The relative weight of the modes in a particular spectrum may depend critically on the electron impact energy. For larger wave vectors beyond q∥>0.35 Å-1 and layers thicker than five atom layers the separate modes merge into a single, broad loss feature. Since the shape and position of the loss feature depend on the electron impact energy, a separation into different modes is nevertheless possible for not too large wave vectors. The spin wave dispersion curves of films grown on W(110) agree with those observed on Cu(111) if one takes into account that on copper the cobalt grows in islands so that the mean height of the islands is higher than the nominal coverage. On films grown on Au(111) the low wave vector spin waves are buried in the high elastic diffuse scattering caused by the considerable disorder in the films. The broader appearance of the spectra at higher wave vectors compared to films grown on W(110) and Cu(111) is quantitatively accounted for by disorder-induced kinematic broadening. Because of the granular growth on copper and gold primarily the spin wave spectrum of cobalt films on W(110) is amenable to quantitative theoretical analysis. Such an analysis is not available at present. We show however, that the dispersion curves are incompatible with the Heisenberg model as long as only a single, layer-independent exchange coupling constant is invoked.

  14. Interface electronic structures of reversible double-docking self-assembled monolayers on an Au(111) surface.

    PubMed

    Zhang, Tian; Ma, Zhongyun; Wang, Linjun; Xi, Jinyang; Shuai, Zhigang

    2014-04-13

    Double-docking self-assembled monolayers (DDSAMs), namely self-assembled monolayers (SAMs) formed by molecules possessing two docking groups, provide great flexibility to tune the work function of metal electrodes and the tunnelling barrier between metal electrodes and the SAMs, and thus offer promising applications in both organic and molecular electronics. Based on the dispersion-corrected density functional theory (DFT) in comparison with conventional DFT, we carry out a systematic investigation on the dual configurations of a series of DDSAMs on an Au(111) surface. Through analysing the interface electronic structures, we obtain the relationship between single molecular properties and the SAM-induced work-function modification as well as the level alignment between the metal Fermi level and molecular frontier states. The two possible conformations of one type of DDSAM on a metal surface reveal a strong difference in the work-function modification and the electron/hole tunnelling barriers. Fermi-level pinning is found to be a key factor to understand the interface electronic properties.

  15. Dehalogenative Homocoupling of Terminal Alkynyl Bromides on Au(111): Incorporation of Acetylenic Scaffolding into Surface Nanostructures.

    PubMed

    Sun, Qiang; Cai, Liangliang; Ma, Honghong; Yuan, Chunxue; Xu, Wei

    2016-07-26

    On-surface C-C coupling reactions of molecular precursors with alkynyl functional groups demonstrate great potential for the controllable fabrication of low-dimensional carbon nanostructures/nanomaterials, such as carbyne, graphyne, and graphdiyne, which demand the incorporation of highly active sp-hybridized carbons. Recently, through a dehydrogenative homocoupling reaction of alkynes, the possibility was presented to fabricate surface nanostructures involving acetylenic linkages, while problems lie in the fact that different byproducts are inevitably formed when triggering the reactions at elevated temperatures. In this work, by delicately designing the molecular precursors with terminal alkynyl bromide, we introduce the dehalogenative homocoupling reactions on the surface. As a result, we successfully achieve the formation of dimer structures, one-dimensional molecular wires and two-dimensional molecular networks with acetylenic scaffoldings on an inert Au(111) surface, where the unexpected C-Au-C organometallic intermediates are also observed. This study further supplements the database of on-surface dehalogenative C-C coupling reactions, and more importantly, it provides us an alternative efficient way for incorporating the acetylenic scaffolding into low-dimensional surface nanostructures. PMID:27326451

  16. Dehalogenative Homocoupling of Terminal Alkynyl Bromides on Au(111): Incorporation of Acetylenic Scaffolding into Surface Nanostructures.

    PubMed

    Sun, Qiang; Cai, Liangliang; Ma, Honghong; Yuan, Chunxue; Xu, Wei

    2016-07-26

    On-surface C-C coupling reactions of molecular precursors with alkynyl functional groups demonstrate great potential for the controllable fabrication of low-dimensional carbon nanostructures/nanomaterials, such as carbyne, graphyne, and graphdiyne, which demand the incorporation of highly active sp-hybridized carbons. Recently, through a dehydrogenative homocoupling reaction of alkynes, the possibility was presented to fabricate surface nanostructures involving acetylenic linkages, while problems lie in the fact that different byproducts are inevitably formed when triggering the reactions at elevated temperatures. In this work, by delicately designing the molecular precursors with terminal alkynyl bromide, we introduce the dehalogenative homocoupling reactions on the surface. As a result, we successfully achieve the formation of dimer structures, one-dimensional molecular wires and two-dimensional molecular networks with acetylenic scaffoldings on an inert Au(111) surface, where the unexpected C-Au-C organometallic intermediates are also observed. This study further supplements the database of on-surface dehalogenative C-C coupling reactions, and more importantly, it provides us an alternative efficient way for incorporating the acetylenic scaffolding into low-dimensional surface nanostructures.

  17. Dynamics of H2 dissociation on the close-packed (111) surface of the noblest metal: H2 + Au(111)

    NASA Astrophysics Data System (ADS)

    Wijzenbroek, Mark; Helstone, Darcey; Meyer, Jörg; Kroes, Geert-Jan

    2016-10-01

    We have performed calculations on the dissociative chemisorption of H2 on un-reconstructed and reconstructed Au(111) with density functional theory, and dynamics calculations on this process on un-reconstructed Au(111). Due to a very late barrier for dissociation, H2 + Au(111) is a candidate H2-metal system for which the dissociative chemisorption could be considerably affected by the energy transfer to electron-hole pairs. Minimum barrier geometries and potential energy surfaces were computed for six density functionals. The functionals tested yield minimum barrier heights in the range of 1.15-1.6 eV, and barriers that are even later than found for the similar H2 + Cu(111) system. The potential energy surfaces have been used in quasi-classical trajectory calculations of the initial (v,J) state resolved reaction probability for several vibrational states v and rotational states J of H2 and D2. Our calculations may serve as predictions for state-resolved associative desorption experiments, from which initial state-resolved dissociative chemisorption probabilities can be extracted by invoking detailed balance. The vibrational efficacy ηv=0→1 reported for D2 dissociating on un-reconstructed Au(111) (about 0.9) is similar to that found in earlier quantum dynamics calculations on H2 + Ag(111), but larger than found for D2 + Cu(111). With the two functionals tested most extensively, the reactivity of H2 and D2 exhibits an almost monotonic increase with increasing rotational quantum number J. Test calculations suggest that, for chemical accuracy (1 kcal/mol), the herringbone reconstruction of Au(111) should be modeled.

  18. Interplay between Self-Assembled Structures and Energy Level Alignment of Benzenediamine on Au(111) Surfaces

    NASA Astrophysics Data System (ADS)

    Li, Guo; Neaton, Jeffrey

    2015-03-01

    Using van der Waals-corrected density functional theory (DFT) calculations, we study the adsorption of benzene-diamine (BDA) molecules on Au(111) surfaces. We find that at low surface coverage, the adsorbed molecules prefer to stay isolated from each other in a monomer phase, due to the inter-molecular dipole-dipole repulsions. However, when the coverage rises above a critical value of 0.9nm-2, the adsorbed molecules aggregate into linear structures via hydrogen bonding between amine groups, consistent with recent experiments [Haxton, Zhou, Tamblyn, et al, Phys. Rev. Lett. 111, 265701 (2013)]. Moreover, we find that these linear structures at high density considerably reduces the Au work function (relative to a monomer phase). Due to reduced surface polarization effects, we estimate that the resonance energy of the highest occupied molecular orbital of the adsorbed BDA molecule relative to the Au Fermi level is significantly lower than the monomer phase by more than 0.5 eV, consistent with the experimental measurements [DellAngela, Kladnik, and Cossaro, et al., Nano Lett. 10, 2470 (2010)]. This work supported by DOE (the JCAP under Award Number DE-SC000499 and the Molecular Foundry of LBNL), and computational resources provided by NERSC.

  19. Six-dimensional quantum dynamics study for the dissociative adsorption of DCl on Au(111) surface

    SciTech Connect

    Liu, Tianhui; Fu, Bina E-mail: zhangdh@dicp.ac.cn; Zhang, Dong H. E-mail: zhangdh@dicp.ac.cn

    2014-04-14

    We carried out six-dimensional quantum dynamics calculations for the dissociative adsorption of deuterium chloride (DCl) on Au(111) surface using the initial state-selected time-dependent wave packet approach. The four-dimensional dissociation probabilities are also obtained with the center of mass of DCl fixed at various sites. These calculations were all performed based on an accurate potential energy surface recently constructed by neural network fitting to density function theory energy points. The origin of the extremely small dissociation probability for DCl/HCl (v = 0, j = 0) fixed at the top site compared to other fixed sites is elucidated in this study. The influence of vibrational excitation and rotational orientation of DCl on the reactivity was investigated by calculating six-dimensional dissociation probabilities. The vibrational excitation of DCl enhances the reactivity substantially and the helicopter orientation yields higher dissociation probability than the cartwheel orientation. The site-averaged dissociation probability over 25 fixed sites obtained from four-dimensional quantum dynamics calculations can accurately reproduce the six-dimensional dissociation probability.

  20. Six-dimensional quantum dynamics study for the dissociative adsorption of DCl on Au(111) surface.

    PubMed

    Liu, Tianhui; Fu, Bina; Zhang, Dong H

    2014-04-14

    We carried out six-dimensional quantum dynamics calculations for the dissociative adsorption of deuterium chloride (DCl) on Au(111) surface using the initial state-selected time-dependent wave packet approach. The four-dimensional dissociation probabilities are also obtained with the center of mass of DCl fixed at various sites. These calculations were all performed based on an accurate potential energy surface recently constructed by neural network fitting to density function theory energy points. The origin of the extremely small dissociation probability for DCl/HCl (v = 0, j = 0) fixed at the top site compared to other fixed sites is elucidated in this study. The influence of vibrational excitation and rotational orientation of DCl on the reactivity was investigated by calculating six-dimensional dissociation probabilities. The vibrational excitation of DCl enhances the reactivity substantially and the helicopter orientation yields higher dissociation probability than the cartwheel orientation. The site-averaged dissociation probability over 25 fixed sites obtained from four-dimensional quantum dynamics calculations can accurately reproduce the six-dimensional dissociation probability.

  1. Correlated motion of electrons on the Au(111) surface: anomalous acoustic surface-plasmon dispersion and single-particle excitations.

    PubMed

    Vattuone, L; Smerieri, M; Langer, T; Tegenkamp, C; Pfnür, H; Silkin, V M; Chulkov, E V; Echenique, P M; Rocca, M

    2013-03-22

    The linear dispersion of the low-dimensional acoustic surface plasmon (ASP) opens perspectives in energy conversion, transport, and confinement far below optical frequencies. Although the ASP exists in a wide class of materials, ranging from metal surfaces and ultrathin films to graphene and topological insulators, its properties are still largely unexplored. Taking Au(111) as a model system, our combined experimental and theoretical study revealed an intriguing interplay between collective and single particle excitations, causing the ASP associated with the Shockley surface state to be embedded within the intraband transitions without losing its sharp character and linear dispersion. PMID:25166849

  2. Influence of the solution pH in the 6-mercaptopurine self-assembled monolayer (6MP-SAM) on a Au(111) single-crystal electrode.

    PubMed

    Madueño, Rafael; García-Raya, Daniel; Viudez, Alfonso J; Sevilla, José M; Pineda, Teresa; Blázquez, Manuel

    2007-10-23

    Self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) have been prepared on a Au(111) single-crystal electrode by immersion of the metal surface in a 100 microM 6MP and 0.01 M HClO4 solution. The 6MP-SAM Au(111) single-crystal electrodes were transferred to the cell and allowed to equilibrate with the different aqueous working solutions before the electrochemical experiments. The influence of the solution pH was studied by cyclic voltammetry, double layer capacitance curves, and electrochemical impedance spectroscopy. The electrochemical behavior of the 6MP-SAM in acetic acid at pH 4 presents important differences in comparison to that obtained in 0.1 M KOH solutions. Cyclic voltammograms for the reductive desorption process in acid medium are broad and show some features that can be explained by a phase transition between a chemisorbed and a physisorbed state of the 6MP molecules. The low solubility of these molecules in acid medium could explain this phenomenon and the readsorption of the complete monolayer when the potential is scanned in the positive direction. The variation of the double-layer capacitance values in the potential range of monolayer stability with the pH suggests that the acid-base chemistry of the 6MP molecules is playing a role. This fact has been studied by following the variations of the electron-transfer rate constant of the highly charged redox probes as are Fe(CN)(6)-3/-4 and Ru(NH3)(6)+3/+2 as a function of solution pH. The apparent surface pKa value for the 6MP-SAM (pKa approximately 8) is explained by the total conversion of the different 6MP tautomers that exist in solution to the thiol species in the adsorbed state. PMID:17902711

  3. Influence of the solution pH in the 6-mercaptopurine self-assembled monolayer (6MP-SAM) on a Au(111) single-crystal electrode.

    PubMed

    Madueño, Rafael; García-Raya, Daniel; Viudez, Alfonso J; Sevilla, José M; Pineda, Teresa; Blázquez, Manuel

    2007-10-23

    Self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) have been prepared on a Au(111) single-crystal electrode by immersion of the metal surface in a 100 microM 6MP and 0.01 M HClO4 solution. The 6MP-SAM Au(111) single-crystal electrodes were transferred to the cell and allowed to equilibrate with the different aqueous working solutions before the electrochemical experiments. The influence of the solution pH was studied by cyclic voltammetry, double layer capacitance curves, and electrochemical impedance spectroscopy. The electrochemical behavior of the 6MP-SAM in acetic acid at pH 4 presents important differences in comparison to that obtained in 0.1 M KOH solutions. Cyclic voltammograms for the reductive desorption process in acid medium are broad and show some features that can be explained by a phase transition between a chemisorbed and a physisorbed state of the 6MP molecules. The low solubility of these molecules in acid medium could explain this phenomenon and the readsorption of the complete monolayer when the potential is scanned in the positive direction. The variation of the double-layer capacitance values in the potential range of monolayer stability with the pH suggests that the acid-base chemistry of the 6MP molecules is playing a role. This fact has been studied by following the variations of the electron-transfer rate constant of the highly charged redox probes as are Fe(CN)(6)-3/-4 and Ru(NH3)(6)+3/+2 as a function of solution pH. The apparent surface pKa value for the 6MP-SAM (pKa approximately 8) is explained by the total conversion of the different 6MP tautomers that exist in solution to the thiol species in the adsorbed state.

  4. Voltammetry and in situ scanning tunnelling spectroscopy of osmium, iron, and ruthenium complexes of 2,2':6',2''-terpyridine covalently linked to Au(111)-electrodes.

    PubMed

    Salvatore, Princia; Hansen, Allan Glargaard; Moth-Poulsen, Kasper; Bjørnholm, Thomas; Nichols, Richard John; Ulstrup, Jens

    2011-08-28

    We have studied self-assembled molecular monolayers (SAMs) of complexes between Os(II)/(III), Fe(II)/(III), and Ru(II)/(III) and a 2,2',6',2''-terpyridine (terpy) derivative linked to Au(111)-electrode surfaces via a 6-acetylthiohexyloxy substituent at the 4'-position of terpy. The complexes were prepared in situ by first linking the terpy ligand to the surface via the S-atom, followed by addition of suitable metal compounds. The metal-terpy SAMs were studied by cyclic voltammetry (CV), and in situ scanning tunnelling microscopy with full electrochemical potential control of substrate and tip (in situ STM). Sharp CV peaks were observed for the Os- and Fe complexes, with interfacial electrochemical electron transfer rate constants of 6-50 s(-1). Well-defined but significantly broader peaks (up to 300 mV) were observed for the Ru-complex. Addition of 2,2'-bipyridine (bipy) towards completion of the metal coordination spheres induced voltammetric sharpening. In situ STM images of single molecular scale strong structural features were observed for the osmium and iron complexes. As expected from the voltammetric patterns, the surface coverage was by far the highest for the Ru-complex which was therefore selected for scanning tunnelling spectroscopy. These correlations displayed a strong peak around the equilibrium potential with systematic shifts with increasing bias voltage, as expected for a sequential two-step in situ ET mechanism.

  5. Fullerene-derivative PC61BM forms three types of phase-pure monolayer on the surface of Au(111)

    NASA Astrophysics Data System (ADS)

    Li, Wen-Jie; Du, Ying-Ying; Zhang, Han-Jie; Chen, Guang-Hua; Sheng, Chun-Qi; Wu, Rui; Wang, Jia-Ou; Qian, Hai-Jie; Ibrahim, Kurash; He, Pi-Mo; Li, Hong-Nian

    2016-12-01

    We have studied the packing structures of C60-derivative PC61BM on the surface of Au(111) in ultrahigh vacuum using scanning tunneling microscopy. The Au(111) has a triangle-like reconstructed surface, which results in some packing structures different from those reported for low coverages. PC61BM can form three types of phase-pure monolayer, namely, the compact straight molecular double-row monolayer, the hexagonal-packing monolayer and the glassy monolayer. The different types of monolayer form for different molecular densities and different annealing temperatures. In addition to the already known inter-molecular interactions (Van de Waals interaction and hydrogen bond), the steric effect of the phenyl-butyric-acid-methyl-ester side tail plays conspicuous role in the molecular self-assembly at high coverages. The steric effect makes it difficult to prepare a hexagonal-packing monolayer at room temperature and decides the instability of the hexagonal-packing monolayer prepared by thermal annealing.

  6. Attosecond interferometry on surfaces: Laser-assisted photoemission from Ag(111) and Au(111) by an XUV pulse train

    NASA Astrophysics Data System (ADS)

    Ambrosio, Marcelo J.; Thumm, Uwe

    2016-05-01

    Motivated by recent RABBITT experiments, we numerically investigated electron emission from metal surfaces by a pulse train of phase coherent attosecond XUV pulses into the assisting electric field of a time-delayed IR laser pulse. From the delay-dependent oscillations of the first-sideband-electron yields in our simulated spectra we deduced the atomic phases of the pulse train's higher harmonic components. These calculations allow us to extract physical properties of solid surfaces, as we numerically demonstrate for the Ag(111) and Au(111) surfaces targeted in, including photoemission from conduction-band and core-level electrons. Supported by the NSF and the Division of Chemical Sciences, Office of the Basic Energy Sciences, Office of Energy Research, US DoE.

  7. Molecular and electronic structure of osmium complexes confined to Au(111) surfaces using a self-assembled molecular bridge

    SciTech Connect

    Llave, Ezequiel de la; Herrera, Santiago E.; Adam, Catherine; Méndez De Leo, Lucila P.; Calvo, Ernesto J.; Williams, Federico J.

    2015-11-14

    The molecular and electronic structure of Os(II) complexes covalently bonded to self-assembled monolayers (SAMs) on Au(111) surfaces was studied by means of polarization modulation infrared reflection absorption spectroscopy, photoelectron spectroscopies, scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. Attachment of the Os complex to the SAM proceeds via an amide covalent bond with the SAM alkyl chain 40° tilted with respect to the surface normal and a total thickness of 26 Å. The highest occupied molecular orbital of the Os complex is mainly based on the Os(II) center located 2.2 eV below the Fermi edge and the LUMO molecular orbital is mainly based on the bipyridine ligands located 1.5 eV above the Fermi edge.

  8. Molecular and electronic structure of osmium complexes confined to Au(111) surfaces using a self-assembled molecular bridge.

    PubMed

    de la Llave, Ezequiel; Herrera, Santiago E; Adam, Catherine; Méndez De Leo, Lucila P; Calvo, Ernesto J; Williams, Federico J

    2015-11-14

    The molecular and electronic structure of Os(II) complexes covalently bonded to self-assembled monolayers (SAMs) on Au(111) surfaces was studied by means of polarization modulation infrared reflection absorption spectroscopy, photoelectron spectroscopies, scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. Attachment of the Os complex to the SAM proceeds via an amide covalent bond with the SAM alkyl chain 40° tilted with respect to the surface normal and a total thickness of 26 Å. The highest occupied molecular orbital of the Os complex is mainly based on the Os(II) center located 2.2 eV below the Fermi edge and the LUMO molecular orbital is mainly based on the bipyridine ligands located 1.5 eV above the Fermi edge. PMID:26567676

  9. Molecular and electronic structure of osmium complexes confined to Au(111) surfaces using a self-assembled molecular bridge

    NASA Astrophysics Data System (ADS)

    de la Llave, Ezequiel; Herrera, Santiago E.; Adam, Catherine; Méndez De Leo, Lucila P.; Calvo, Ernesto J.; Williams, Federico J.

    2015-11-01

    The molecular and electronic structure of Os(II) complexes covalently bonded to self-assembled monolayers (SAMs) on Au(111) surfaces was studied by means of polarization modulation infrared reflection absorption spectroscopy, photoelectron spectroscopies, scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. Attachment of the Os complex to the SAM proceeds via an amide covalent bond with the SAM alkyl chain 40° tilted with respect to the surface normal and a total thickness of 26 Å. The highest occupied molecular orbital of the Os complex is mainly based on the Os(II) center located 2.2 eV below the Fermi edge and the LUMO molecular orbital is mainly based on the bipyridine ligands located 1.5 eV above the Fermi edge.

  10. Grafting derivatives of Mn6 single-molecule magnets with high anisotropy energy barrier on Au111 surface.

    PubMed

    Moro, F; Corradini, V; Evangelisti, M; De Renzi, V; Biagi, R; del Pennino, U; Milios, C J; Jones, L F; Brechin, E K

    2008-08-14

    We study the magnetic properties of two new functionalized single-molecule magnets belonging to the Mn 6 family (general formula [Mn (III)6O2(R-sao)6(O2C-th)2L(4-6)], where R=H (1) or Et (2), HO2C-th=3-thiophene carboxylic acid, L=EtOH, H2O and saoH2 is salicylaldoxime) and their grafting on the Au(111) surface. Complex 1 exhibits spin ground-state S=4, as the result of ferromagnetic coupling between the two antiferromagnetic Mn (III) 3 triangles, while slight structural changes in complex 2, switch the dominant magnetic exchange interactions from anti- to ferromagnetic, enhancing the spin ground-state to S=12 and, consequently, the effective energy barrier for the relaxation of magnetization. Direct-current and alternating-current magnetic susceptibility measurements show that the functionalized complexes preserve the main magnetic properties of the corresponding not-functionalized Mn 6 clusters (i.e., total spin value and magnetic behavior as a function of temperature), though a reduction of the anisotropy barrier is observed in complex 2. For both complexes, the -O2C-th functionalization allows the direct grafting on Au(111) surface by liquid-phase deposition. X-ray photoemission spectroscopy demonstrates that the stoichiometry of the molecular cores is preserved after grafting. Scanning tunneling microscopy (STM) reveals a sub-monolayer distribution of isolated clusters with a slightly higher coverage for complex 1. The cluster stability in the STM images and the S-2p energy positions demonstrate, for both derivatives, the strength of the grafting with the gold surface.

  11. The Synthesis of Diquinone and Dihydroquinone Derivatives of Calix[4]arene and Electrochemical Characterization on Au(111) surface.

    PubMed

    Genorio, Boštjan

    2016-01-01

    Several new electroactive diquinone and dihydroquinone derivatives of calix[4]arene bearing anchor functional groups were designed, synthesized and characterized. A method for selective protection of the hydroquinone -OH groups with trimethylsilyl groups (TMS) either on lower-rim or on upper-rim was developed. Four selected molecules - with sulfide anchor groups and carboxylic anchor groups - were adsorbed onto Au(111) single crystal surface using ex-situ and insitu self-assembly methods. Adsorbed molecules were then electrochemically probed with cyclic voltammetry. All adsorbed molecules showed redox response which changed during cycling. After conditioning CVs stabilized and showed two distinct current peaks for all molecules. Synthesized and electrochemically probed molecules are of interest to: Li-ion batteries (as cathode materials and overcharge protection), beyond Li-ion batteries and redox-flow batteries. PMID:27640377

  12. Grafting of functionalized [Fe(III)(salten)] complexes to Au(111) surfaces via thiolate groups: surface spectroscopic characterization and comparison of different linker designs.

    PubMed

    Jacob, Hanne; Kathirvel, Ketheeswari; Petersen, Finn; Strunskus, Thomas; Bannwarth, Alexander; Meyer, Sven; Tuczek, Felix

    2013-07-01

    Functionalization of surfaces with spin crossover complexes is an intensively studied topic. Starting from dinuclear iron(III)-salten complexes [Fe(salten)(pyS)]2(BPh4)2 and [Fe(thiotolylsalten)(NCS)]2 with disulfide-containing bridging ligands, corresponding mononuclear complexes [Fe(salten)(pyS)](+) and [Fe(thiotolylsalten)(NCS)] are covalently attached to Au(111) surfaces (pySH, pyridinethiol; salten, bis(3-salicylidene-aminopropyl)amine). The adsorbed monolayers are investigated by infrared reflection absorption spectroscopy (IRRAS) in combination with X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS). Comparison of the surface vibrational spectra with bulk data allows us to draw conclusions with respect to the geometry of the adsorbed complexes. An anomaly is observed in the spectra of the surface-adsorbed monolayer of [Fe(salten)(pyS)](+), which suggests that the salten ligand is partially decoordinated from the Fe(III) center and one of its phenolate arms binds to the Au(111) surface. For complex [Fe(thiotolylsalten)(NCS)] that is bound to the Au(111) surface via a thiolate-functionalized salten ligand, this anomaly is not observed, which indicates that the coordination sphere of the complex in the bulk is retained on the surface. The implications of these results with respect to the preparation of surface-adsorbed monolayers of functional transition-metal complexes are discussed.

  13. Redox-switching in a viologen-type adlayer: an electrochemical shell-isolated nanoparticle enhanced Raman spectroscopy study on Au(111)-(1×1) single crystal electrodes.

    PubMed

    Liu, Bo; Blaszczyk, Alfred; Mayor, Marcel; Wandlowski, Thomas

    2011-07-26

    We reported the first application of in situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) to an interfacial redox reaction under electrochemical conditions. We construct gap-mode sandwich structures composed of a thiol-terminated HS-6V6H viologen adlayer immobilized on a single crystal Au(111)-(1×1) electrode and covered by Au(60 nm)@SiO(2) core-shell nanoparticles acting as plasmonic antennas. We observed high-quality, potential-dependent Raman spectra of the three viologen species V(2+), V(+●), and V(0) on a well-defined Au(111) substrate surface and could map their potential-dependent evolution. Comparison with experiments on powder samples revealed an enhancement factor of the nonresonant Raman modes of ∼3 × 10(5), and up to 9 × 10(7) for the resonance modes. The study illustrates the unique capability of SHINERS and its potential in the entire field of electrochemical surface science to explore structures and reaction pathways on well-defined substrate surfaces, such as single crystals, for molecular, (electro-)catalytic, bioelectrochemical systems up to fundamental double layer studies at electrified solid/liquid interfaces.

  14. Redox-switching in a viologen-type adlayer: an electrochemical shell-isolated nanoparticle enhanced Raman spectroscopy study on Au(111)-(1×1) single crystal electrodes.

    PubMed

    Liu, Bo; Blaszczyk, Alfred; Mayor, Marcel; Wandlowski, Thomas

    2011-07-26

    We reported the first application of in situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) to an interfacial redox reaction under electrochemical conditions. We construct gap-mode sandwich structures composed of a thiol-terminated HS-6V6H viologen adlayer immobilized on a single crystal Au(111)-(1×1) electrode and covered by Au(60 nm)@SiO(2) core-shell nanoparticles acting as plasmonic antennas. We observed high-quality, potential-dependent Raman spectra of the three viologen species V(2+), V(+●), and V(0) on a well-defined Au(111) substrate surface and could map their potential-dependent evolution. Comparison with experiments on powder samples revealed an enhancement factor of the nonresonant Raman modes of ∼3 × 10(5), and up to 9 × 10(7) for the resonance modes. The study illustrates the unique capability of SHINERS and its potential in the entire field of electrochemical surface science to explore structures and reaction pathways on well-defined substrate surfaces, such as single crystals, for molecular, (electro-)catalytic, bioelectrochemical systems up to fundamental double layer studies at electrified solid/liquid interfaces. PMID:21634391

  15. First-principles investigations of the structure and stability of oxygen adsorption and surface oxide formation at Au(111)

    NASA Astrophysics Data System (ADS)

    Shi, Hongqing; Stampfl, Catherine

    2007-08-01

    We perform density-functional theory calculations to investigate the adsorption of oxygen at the Au(111) surface, including on-surface, subsurface, and surface oxide formation. We find that atomic oxygen adsorbs weakly on the surface and is barely stable with respect to molecular oxygen, while pure subsurface adsorption is only metastable. Interestingly, however, we find that the most favorable structure investigated involves a thin surface-oxide-like configuration, where the oxygen atoms are quasithreefold-coordinated to gold atoms, and the gold atoms of the surface layer are twofold, linearly coordinated to oxygen atoms. By including the effect of temperature and oxygen pressure through the description of ab initio atomistic thermodynamics, we find that this configuration is the most stable for realistic catalytic temperatures and pressures, e.g., for low-temperature oxidation reactions, and is predicted to be stable up to temperatures of around 420K at atmospheric pressure. This gives support to the notion that oxidized Au, or surface-oxide-like regions, could play a role in the behavior of oxide-supported nanogold catalysts.

  16. Monolayer Phases of a Dipolar Perylene Derivative on Au(111) and Surface Potential Build-Up in Multilayers.

    PubMed

    Niederhausen, Jens; Kersell, Heath R; Christodoulou, Christos; Heimel, Georg; Wonneberger, Henrike; Müllen, Klaus; Rabe, Jürgen P; Hla, Saw-Wai; Koch, Norbert

    2016-04-19

    9-(Bis-p-tert-octylphenyl)-amino-perylene-3,4-dicarboxy anhydride (BOPA-PDCA) is a strongly dipolar molecule representing a group of asymmetrically substituted perylenes that are employed in dye-sensitized solar cells and hold great promise for discotic liquid crystal applications. Thin BOPA-PDCA films with orientated dipole moments can potentially be used to tune the energy-level alignment in electronic devices and store information. To help assessing these prospects, we here elucidate the molecular self-assembly and electronic structure of BOPA-PCDA employing room temperature scanning tunneling microscopy and spectroscopy in combination with ultraviolet and X-ray photoelectron spectroscopies. BOPA-PCDA monolayers on Au(111) exclusively form in-plane antiferroelectric phases. The molecular arrangements, the increase of the average number of molecules per unit cell via ripening, and the rearrangement upon manipulation with the STM tip indicate an influence of the dipole moment on the molecular assembly and the rearrangement. A slightly preferred out-of-plane orientation of the molecules in the multilayer induces a surface potential of 1.2 eV. This resembles the giant surface potential effect that was reported for vacuum-deposited tris(8-hydroxyquinoline)aluminum and deemed applicable for data storage. Notably, the surface potential in the case of BOPA-PDCA can in part be reversibly removed by visible light irradiation. PMID:26991048

  17. Electron emission spectra of thermal collisions of He metastable atoms with Au(111) and Pt(111) surfaces: Evidence for Penning ionization

    SciTech Connect

    Masuda, S.; Sasaki, K.; Sogo, M.; Aoki, M.; Morikawa, Y.

    2009-10-15

    Electron emission spectra obtained by thermal collisions of He*(2{sup 1}S and 2{sup 3}S) atoms with Au(111) and Pt(111) surfaces were measured to clarify the electronically excited atom-metal interactions. It has been recognized that the metastable atoms de-excite on ordinary noble- and transition-metal surfaces via resonance ionization (RI) followed by Auger neutralization (AN) without no indication of Penning ionization (PI). Our data show that this traditional criterion partially breaks down in the He*-Au(111) collision system. The local electronic states near the surface were examined by first-principles calculations using density functional theory. It reveals that the itinerant sp states are significantly spilled out toward the vacuum compared to the localized 5d states, and their asymptotic features play a crucial role in determining the branching ratio between PI and RI+AN.

  18. Final rotational state distributions from NO(vi = 11) in collisions with Au(111): the magnitude of vibrational energy transfer depends on orientation in molecule-surface collisions.

    PubMed

    Krüger, Bastian C; Bartels, Nils; Wodtke, Alec M; Schäfer, Tim

    2016-06-01

    When NO molecules collide at a Au(111) surface, their interaction is controlled by several factors; especially important are the molecules' orientation with respect to the surface (N-first vs. O-first) and their distance of closest approach. In fact, the former may control the latter as N-first orientations are attractive and O-first orientations are repulsive. In this work, we employ electric fields to control the molecules' incidence orientation in combination with rotational rainbow scattering detection. Specifically, we report final rotational state distributions of oriented NO(vi = 11) molecules scattered from Au(111) for final vibrational states between vf = 4 and 11. For O-first collisions, the interaction potential is highly repulsive preventing the close approach and scattering results in high-J rainbows. By contrast, these rainbows are not seen for the more intimate collisions possible for attractive N-first orientations. In this way, we reveal the influence of orientation and the distance of closest approach on vibrational relaxation of NO(vi = 11) in collisions with a Au(111) surface. We also elucidate the influence of steering forces which cause the O-first oriented molecules to rotate to an N-first orientation during their approach to the surface. The experiments show that when NO collides at the surface with the N-atom first, on average more than half of the initial vibrational energy is lost; whereas O-first oriented collisions lose much less vibrational energy. These observations qualitatively confirm theoretical predictions of electronically non-adiabatic NO interactions at Au(111). PMID:27193070

  19. Effect of Dispersion on Surface Interactions of Cobalt(II) Octaethylporphyrin Monolayer on Au(111) and HOPG(0001) Substrates: a Comparative First Principles Study

    SciTech Connect

    Chilukuri, Bhaskar; Mazur, Ursula; Hipps, Kerry W.

    2014-07-21

    A density functional theory study of a cobalt(II) octaethylporphyrin (CoOEP) monolayer on Au(111) and HOPG(0001) surfaces was performed under periodic boundary conditions. Calculations with and without dispersion corrections are performed and the effect of van der Waals forces on the interface properties is analyzed. Calculations have determined that the CoOEP molecule tends to bind at the 3-fold and the 6-fold center sites on Au(111) and HOPG(0001), respectively. Geometric optimizations at the center binding sites have indicated that the porphyrin molecules (in the monolayer) lie flat on both substrates. Calculations also reveal that the CoOEP monolayer binds slightly more strongly to Au(111) than to HOPG(0001). Charge density difference plots disclose that charge is redistributed mostly around the porphyrin plane and the first layer of the substrates. Dispersion interactions cause a larger substrate to molecule charge pushback on Au(111) than on HOPG. CoOEP adsorption tends to lower the work functions of either substrate, qualitatively agreeing with the experimental photoelectron spectroscopic data. Comparison of the density of states (DOS) of the isolated CoOEP molecule with that on gold and HOPG substrates showed significant band shifts around the Fermi energy due to intermolecular orbital hybridization. Simulated STM images were plotted with the Tersoff–Hamann approach using the local density of states, which also agree with the experimental results. This study elucidates the role of dispersion for better describing porphyrin–substrate interactions. A DFT based overview of geometric, adsorption and electronic properties of a porphyrin monolayer on conductive surfaces is presented.

  20. Effect of dispersion on surface interactions of cobalt(II) octaethylporphyrin monolayer on Au(111) and HOPG(0001) substrates: a comparative first principles study.

    PubMed

    Chilukuri, Bhaskar; Mazur, Ursula; Hipps, K W

    2014-07-21

    A density functional theory study of a cobalt(II) octaethylporphyrin (CoOEP) monolayer on Au(111) and HOPG(0001) surfaces was performed under periodic boundary conditions. Calculations with and without dispersion corrections are performed and the effect of van der Waals forces on the interface properties is analyzed. Calculations have determined that the CoOEP molecule tends to bind at the 3-fold and the 6-fold center sites on Au(111) and HOPG(0001), respectively. Geometric optimizations at the center binding sites have indicated that the porphyrin molecules (in the monolayer) lie flat on both substrates. Calculations also reveal that the CoOEP monolayer binds slightly more strongly to Au(111) than to HOPG(0001). Charge density difference plots disclose that charge is redistributed mostly around the porphyrin plane and the first layer of the substrates. Dispersion interactions cause a larger substrate to molecule charge pushback on Au(111) than on HOPG. CoOEP adsorption tends to lower the work functions of either substrate, qualitatively agreeing with the experimental photoelectron spectroscopic data. Comparison of the density of states (DOS) of the isolated CoOEP molecule with that on gold and HOPG substrates showed significant band shifts around the Fermi energy due to intermolecular orbital hybridization. Simulated STM images were plotted with the Tersoff-Hamann approach using the local density of states, which also agree with the experimental results. This study elucidates the role of dispersion for better describing porphyrin-substrate interactions. A DFT based overview of geometric, adsorption and electronic properties of a porphyrin monolayer on conductive surfaces is presented.

  1. Studying Two-Dimensional Zeolites with the Tools of Surface Science: MFI Nanosheets on Au(111)

    DOE PAGES

    J. D. Kestell; Zhong, J. Q.; Shete, M.; Waluyo, I.; Sadowski, J. T.; Stacchiola, D. J.; Tsapatsis, M.; Boscoboinik, J. A.

    2016-07-26

    While surface science has provided fundamental insights into a variety a materials, the most used catalysts in the industry, namely zeolites, still remain a challenge. The recent preparation of two-dimensional versions of MFI zeolite frameworks and the possibility of their deposition on electrically conductive supports provides for the first time a viable strategy to perform detailed studies on industrially relevant zeolites using the vast toolkit of surface science. In this work we demonstrate the use of infrared reflection absorption spectroscopy (IRRAS) and synchrotron-based x-ray photoelectron spectroscopy (XPS) to study these materials. Furthermore, polarization modulation IRRAS is used to study themore » adsorption of methanol and its effect in phonon vibrations of the zeolite framework. The possibility of using surface science methods, in particular under ambient pressure conditions, for the study of well-defined zeolites and other microporous structures opens new avenues to understand structural and mechanistic aspects of these materials as catalysts, adsorbents and molecular sieves.« less

  2. Decompositional, incommensurate growth of Ferrocene molecules on a Au(111) surface

    SciTech Connect

    K.-F. Braun, V. Iancu, N. Pertaya, K.-H. Rieder and S.-W. Hla

    2006-07-01

    Deviating from the common growth mode of molecular films of organic molecules where the adsorbates remain intact, we observe an essentially different growth behavior for metalocenes with a low temperature scanning tunneling microscope. Ferrocene molecules adsorb dissociatively and form a two layer structure after being decomposed into fragments. The toplayer unit cell is composed of two tilted cyclopentadienyl rings, while the first layer consists of the remaining fragments. Surprisingly a fourfold symmetry is observed for the top layer while the first layer displays threefold symmetry elements. It is this symmetry mismatch which induces an incommensurability between these layers in all except one surface direction. The toplayer is weakly bonded and has an antiferromagnetic groundstate as calculated by local spin density functional approximation.

  3. Acetaldehyde partial oxidation on the Au(111) model catalyst surface: C-C bond activation and formation of methyl acetate as an oxidative coupling product

    NASA Astrophysics Data System (ADS)

    Karatok, Mustafa; Vovk, Evgeny I.; Shah, Asad A.; Turksoy, Abdurrahman; Ozensoy, Emrah

    2015-11-01

    Partial oxidation of acetaldehyde (CH3CHO) on the oxygen pre-covered Au(111) single crystal model catalyst was investigated via Temperature Programmed Desorption (TPD) and Temperature Programmed Reaction Spectroscopy (TPRS) techniques, where ozone (O3) was utilized as the oxygen delivery agent providing atomic oxygen to the reacting surface. We show that for low exposures of O3 and small surface oxygen coverages, two partial oxidation products namely, methyl acetate (CH3COOCH3) and acetic acid (CH3COOH) can be generated without the formation of significant quantities of carbon dioxide. The formation of methyl acetate as the oxidative coupling reaction product implies that oxygen pre-covered Au(111) single crystal model catalyst surface can activate C-C bonds. In addition to the generation of these products; indications of the polymerization of acetaldehyde on the gold surface were also observed as an additional reaction route competing with the partial and total oxidation pathways. The interplay between the partial oxidation, total oxidation and polymerization pathways reveals the complex catalytic chemistry associated with the interaction between the acetaldehyde and atomic oxygen on catalytic gold surfaces.

  4. Comparing Ullmann Coupling on Noble Metal Surfaces: On-Surface Polymerization of 1,3,6,8-Tetrabromopyrene on Cu(111) and Au(111).

    PubMed

    Pham, Tuan Anh; Song, Fei; Nguyen, Manh-Thuong; Li, Zheshen; Studener, Florian; Stöhr, Meike

    2016-04-18

    The on-surface polymerization of 1,3,6,8-tetrabromopyrene (Br4 Py) on Cu(111) and Au(111) surfaces under ultrahigh vacuum conditions was investigated by a combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. Deposition of Br4 Py on Cu(111) held at 300 K resulted in a spontaneous debromination reaction, generating the formation of a branched coordination polymer network stabilized by C-Cu-C bonds. After annealing at 473 K, the C-Cu-C bonds were converted to covalent C-C bonds, leading to the formation of a covalently linked molecular network of short oligomers. In contrast, highly ordered self-assembled two-dimensional (2D) patterns stabilized by both Br-Br halogen and Br-H hydrogen bonds were observed upon deposition of Br4 Py on Au(111) held at 300 K. Subsequent annealing of the sample at 473 K led to a dissociation of the C-Br bonds and the formation of disordered metal-coordinated molecular networks. Further annealing at 573 K resulted in the formation of covalently linked disordered networks. Importantly, we found that the chosen substrate not only plays an important role as catalyst for the Ullmann reaction, but also influences the formation of different types of intermolecular bonds and thus, determines the final polymer network morphology. DFT calculations further support our experimental findings obtained by STM and XPS and add complementary information on the reaction pathway of Br4 Py on the different substrates.

  5. Potential Dependent Adlayer Structures of a Sulfur-Covered Au(111) Electrode in Alkaline Solution: An in Situ STM Study

    SciTech Connect

    Schlaup, C.; Friebel, D.; Broekmann, P.; Wandelt, K.; /Bonn U. /SLAC, SSRL

    2009-05-11

    A sulfur-covered Au(1 1 1) electrode ({Theta}{sub S} = 0.33 ML) subjected to potential increases in an S-free NaOH solution, i.e., at a fixed S coverage, leads to the reversible formation of a rhombic phase at anodic potentials. The local S coverage increase which is required for the formation of the rhombic phase results from a coverage decrease within the ({radical}3 x {radical}3)R30{sup o} regions, where single-S-atom-defects and, in later stages, S vacancy islands are formed. Due to the high potential induced S-Au bond strength, it was possible for the first time to retain islands of this incomplete ({radical}3 x {radical}3)R30{sup o} S layer in the 2D solid state. Furthermore, a Au mass transport was observed during the growth of the rhombic phase. This clearly calls for a reinterpretation of its chemical nature.

  6. Intermixed adatom and surface-bound adsorbates in regular self-assembled monolayers of racemic 2-butanethiol on Au(111).

    PubMed

    Ouyang, Runhai; Yan, Jiawei; Jensen, Palle S; Ascic, Erhad; Gan, Shiyu; Tanner, David; Mao, Bingwei; Niu, Li; Zhang, Jingdong; Tang, Chunguang; Hush, Noel S; Reimers, Jeffrey R; Ulstrup, Jens

    2015-04-01

    In situ scanning tunneling microscopy combined with density functional theory molecular dynamics simulations reveal a complex structure for the self-assembled monolayer (SAM) of racemic 2-butanethiol on Au(111) in aqueous solution. Six adsorbate molecules occupy a (10×√3)R30° cell organized as two RSAuSR adatom-bound motifs plus two RS species bound directly to face-centered-cubic and hexagonally close-packed sites. This is the first time that these competing head-group arrangements have been observed in the same ordered SAM. Such unusual packing is favored as it facilitates SAMs with anomalously high coverage (30%), much larger than that for enantiomerically resolved 2-butanethiol or secondary-branched butanethiol (25%) and near that for linear-chain 1-butanethiol (33%).

  7. Mechanical and charge transport properties of alkanethiol self-assembled monolayers on Au (111) surface: The Role of Molecular Tilt

    SciTech Connect

    Mulleregan, Alice; Qi, Yabing; Ratera, Imma; Park, Jeong Y.; Ashby, Paul D.; Quek, Su Ying; Neaton, J. B.; Salmeron, Miquel

    2007-11-12

    The relationship between charge transport and mechanical properties of alkanethiol self-assembled monolayers (SAM) on Au(111) films has been investigated using an atomic force microscope with a conductive tip. Molecular tilts induced by the pressure applied by the tip cause stepwise increases in film conductivity. A decay constant {beta} = 0.57 {+-} 0.03 {angstrom}{sup -1} was found for the current passing through the film as a function of tip-substrate separation due to this molecular tilt. This is significantly smaller than the value of {approx} 1 {angstrom}{sup -1} found when the separation is changed by changing the length of the alkanethiol molecules. Calculations indicate that for isolated dithiol molecules S-bonded to hollow sites, the junction conductance does not vary significantly as a function of molecular tilt. The impact of S-Au bonding on SAM conductance is discussed.

  8. Au enrichment and vertical relaxation of the Cu3Au (111 ) surface studied by normal-incidence x-ray standing waves

    NASA Astrophysics Data System (ADS)

    Bauer, O.; Schmitz, C. H.; Ikonomov, J.; Willenbockel, M.; Soubatch, S.; Tautz, F. S.; Sokolowski, M.

    2016-06-01

    We have investigated the Cu3Au (111 ) surface, prepared under ultrahigh vacuum conditions by sputtering and annealing, by low energy electron diffraction (LEED), scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy, and normal incidence x-ray standing waves (NIXSW). We find the surface to be depleted with Cu and enriched with Au at the same time, yielding a nominal Cu:Au ratio of 0.61:0.39 in the topmost layer. The STM images reveal that the first layer is nearly closely filled with atoms and contains a small amount of vacancies with an area concentration of about 5 % . Together with the Au enrichment, these cause local short-range disorder of the Au p (2 ×2 ) reconstruction. From this data, the average stoichiometry of the p (2 ×2 ) surface unit cell is estimated at C u2.22A u1.44□0.20 (instead of C u3.00A u1.00□0.00 of the ideal surface; □ denotes an atomic vacancy site). From NIXSW we find a significant outward relaxation of both the Cu and Au atoms of the topmost layer by 0.28 Å and 0.33 Å, which corresponds to 13 % and 15 % of the (111) bulk layer spacing of C u3Au . We suggest that this originates from a widening of the first/second layer spacing, by 6.8 % and 8.8 % for the Cu and Au atoms, respectively, plus an additional rigid increase in the second/third layer spacing by 6.2 % . We explain this by steric repulsions between Au atoms of the topmost layer, replacing smaller Cu atoms, and Au atoms in the second layer in combination with disorder. Finally, a lateral reconstruction, similar to that on the Au(111) surface, but with a much larger periodicity of 290 Å, is identified from LEED.

  9. Electrochemical Potential Stabilization of Reconstructed Au(111) Structure by Monolayer Coverage with Graphene.

    PubMed

    Yasuda, Satoshi; Kumagai, Ryota; Nakashima, Koji; Murakoshi, Kei

    2015-09-01

    The electrochemical properties of a monolayer graphene grown on a Au(111) electrode were studied using cyclic voltammetry (CV) and electrochemical scanning tunneling microscopy (EC-STM). CV and EC-STM measurements in 0.1 M H2SO4 aqueous solution revealed that graphene grown on the reconstructed (22 × √3) Au(111) structure effectively inhibited potential-induced structural transitions between reconstructed (22 × √3) and unreconstructed (1 × 1), and the adsorption/desorption of SO4(2-) ions, which are intrinsic behavior of the bare Au(111) surface. The underlying reconstructed structure was significantly stabilized by covering with monolayer graphene over a wide potential range between -0.2 V and +1.35 V vs Ag/AgCl (saturated KCl), which is much wider than that for bare Au(111) (-0.2 to + 0.35 V vs Ag/AgCl (saturated KCl)). Such high stability has not been reported to date; therefore, these results are considered to be important for understanding the fundamentals of surface reconstruction and also serve to open a new branch of electrochemistry related to graphene/metal-electrolyte interfaces. PMID:26279244

  10. SAM Surface Domains of (11-Mercaptooundecyl)-N,N,N-Trimethlyammonium Bromide and Dodecanthiol Mixtures on Au(111) Investigated Via AFM

    NASA Astrophysics Data System (ADS)

    Schell, Michael; Senevirathne, Indrajith C.; Murphy, John; Foster, Albert, III

    2014-03-01

    Charged/functional SAM (Self Assembled Monolayer) surfaces have many potential applications in various domains including devices for bioengineering. These surfaces also may be interesting because of the complex physics and chemistry of the charged/conductive molecular layers. The SAM used in our study is (11-Mercaptoundecyl)-N,N,N-trimethylammonium bromide, which have shown conductive properties. The substrate support for SAMs are by Au(111) on mica. Crystalline substrate Au surface was established via in-house hydrogen flame annealing. Thiolated solutions of (11-Mercaptoundecyl)-N,N,N-trimethylammonium bromide and dodecanthiol of varying concentration ratios were used as media for self assembly. Total molarity of the solutions was kept at 5mM for with the time for self assembly at 24 hours or more. Morphology, structure and conductivity characteristics were measured via tapping mode Atomic Force Microscopy (AFM) in the topography/phase imaging and Scanning Tunneling Microscopy (STM) in constant current mode. Data will be used to assess the surface structure of these systems.

  11. Van Der Waals-Corrected Density Functional Theory Simulation of Adsorption Processes on Noble-Metal Surfaces: Xe on Ag(111), Au(111), and Cu(111)

    NASA Astrophysics Data System (ADS)

    Silvestrelli, Pier Luigi; Ambrosetti, Alberto

    2016-10-01

    The DFT/vdW-WF2s1 method based on the generation of localized Wannier functions, recently developed to include the van der Waals interactions in the density functional theory and describe adsorption processes on metal surfaces by taking metal-screening effects into account, is applied to the case of the interaction of Xe with noble-metal surfaces, namely Ag(111), Au(111), and Cu(111). The study is also repeated by adopting the DFT/vdW-QHO-WF variant relying on the quantum harmonic oscillator model which describes well many body effects. Comparison of the computed equilibrium binding energies and distances, and the C_3 coefficients characterizing the adatom-surface van der Waals interactions, with available experimental and theoretical reference data shows that the methods perform well and elucidates the importance of properly including screening effects. The results are also compared with those obtained by other vdW-corrected DFT schemes, including PBE-D, vdW-DF, vdW-DF2, rVV10, and by the simpler local density approximation and semi-local (PBE) generalized gradient approximation approaches.

  12. Atomic and molecular adsorption on Au(111)

    SciTech Connect

    Santiago-Rodríguez, Yohaselly; Herron, Jeffrey A.; Curet-Arana, María C.; Mavrikakis, Manos

    2014-09-01

    Periodic self-consistent density functional theory (DFT-GGA) calculations were used to study the adsorption of several atomic species, molecular species and molecular fragments on the Au(111) surface with a coverage of 1/4 monolayer (ML). Binding geometries, binding energies, and diffusion barriers were calculated for 27 species. Furthermore, we calculated the surface deformation energy associated with the binding events. The binding strength for all the analyzed species can be ordered as follows: NH3 < NO < CO < CH3 < HCO < NH2 < COOH < OH < HCOO < CNH2 < H < N < NH < NOH < COH < Cl,< HCO3 < CH2 < CN b HNO < O < F < S < C < CH. Although the atomic species preferred to bind at the three-fold fcc site, no tendency was observed in site preference for the molecular species and fragments. The intramolecular and adsorbate-surface vibrational frequencies were calculated for all the adsorbates on their most energetically stable adsorption site. Most of the theoretical binding energies and frequencies agreed with experimental values reported in the literature. In general, the values obtained with the PW91 functional are more accurate than RPBE in reproducing these experimental binding energies. The energies of the adsorbed species were used to calculate the thermochemical potential energy surfaces for decomposition of CO, NO, N2, NH3 and CH4, oxidation of CO, and hydrogenation of CO, CO2 and NO, giving insight into the thermochemistry of these reactions on gold nanoparticles. These potential energy surfaces demonstrated that: the decomposition of species is not energetically favorable on Au(111); the desorption of NH3, NO and CO are more favorable than their decomposition; the oxidation of CO and hydrogenation of CO and NO on Au(111) to form HCO and HNO, respectively, are also thermodynamically favorable.

  13. Surface Structure and Chemical Switching of Thioctic Acid Adsorbed on Au(111) as Observed Using Near-Edge X-ray Absorption Fine Structure

    SciTech Connect

    Meulenberg, R W; van Buuren, T; Vance, A L; Terminello, L J; Willey, T M; Bostedt, C; Fadley, C S

    2004-01-06

    Thioctic acid (alpha-lipoic acid) is a molecule with a large disulfide-containing base, a short alkyl-chain with four CH{sub 2} units, and a carboxyl termination. Self-assembled monolayer (SAM) films of thioctic acid adsorbed on Au(111) have been investigated with near-edge x-ray absorption fine structure (NEXAFS) spectroscopy and x-ray photoelectron spectroscopy (XPS) to determine film quality, bonding and morphology. Using standard preparation protocols for SAMs, that is, dissolving thioctic acid in ethanol and exposing gold to the solution, results in poor films. These films are highly disordered, contain a mixture of carboxyl and carboxylate terminations, have more than monolayer coverage, and exhibit unbound disulfide. Conversely, forming films by dissolving 1 mmol thioctic acid into 5% acetic acid in ethanol (as previously reported with carboxyl-terminated alkyl-thiols) forms ordered monolayers with small amounts of unbound sulfur. NEXAFS indicates tilted over endgroups with the carboxyl group normal on average 38{sup o} from the surface normal. Slight dichroism in other features indicates alkyl chains statistically more upright than prostrate on the surface. Reflection-absorption Fourier transform infrared (RA-FTIR) spectra indicate hydrogen bonding between neighboring molecules. In such well-formed monolayers, a stark reorientation occurs upon deprotonation of the endgroup by rinsing in a KOH solution. The carboxylate plane normal is now about 66{sup o} from sample normal, a much more upright orientation. Data indicate this reorientation may also cause a more upright orientation to the alkyl portion of the molecules.

  14. An accurate full-dimensional potential energy surface for H-Au(111): Importance of nonadiabatic electronic excitation in energy transfer and adsorption.

    PubMed

    Janke, Svenja M; Auerbach, Daniel J; Wodtke, Alec M; Kandratsenka, Alexander

    2015-09-28

    We have constructed a potential energy surface (PES) for H-atoms interacting with fcc Au(111) based on fitting the analytic form of the energy from Effective Medium Theory (EMT) to ab initio energy values calculated with density functional theory. The fit used input from configurations of the H-Au system with Au atoms at their lattice positions as well as configurations with the Au atoms displaced from their lattice positions. It reproduces the energy, in full dimension, not only for the configurations used as input but also for a large number of additional configurations derived from ab initio molecular dynamics (AIMD) trajectories at finite temperature. Adiabatic molecular dynamics simulations on this PES reproduce the energy loss behavior of AIMD. EMT also provides expressions for the embedding electron density, which enabled us to develop a self-consistent approach to simulate nonadiabatic electron-hole pair excitation and their effect on the motion of the incident H-atoms. For H atoms with an energy of 2.7 eV colliding with Au, electron-hole pair excitation is by far the most important energy loss pathway, giving an average energy loss ≈3 times that of the adiabatic case. This increased energy loss enhances the probability of the H-atom remaining on or in the Au slab by a factor of 2. The most likely outcome for H-atoms that are not scattered also depends prodigiously on the energy transfer mechanism; for the nonadiabatic case, more than 50% of the H-atoms which do not scatter are adsorbed on the surface, while for the adiabatic case more than 50% pass entirely through the 4 layer simulation slab.

  15. An accurate full-dimensional potential energy surface for H–Au(111): Importance of nonadiabatic electronic excitation in energy transfer and adsorption

    SciTech Connect

    Janke, Svenja M.; Auerbach, Daniel J.; Kandratsenka, Alexander; Wodtke, Alec M.

    2015-09-28

    We have constructed a potential energy surface (PES) for H-atoms interacting with fcc Au(111) based on fitting the analytic form of the energy from Effective Medium Theory (EMT) to ab initio energy values calculated with density functional theory. The fit used input from configurations of the H–Au system with Au atoms at their lattice positions as well as configurations with the Au atoms displaced from their lattice positions. It reproduces the energy, in full dimension, not only for the configurations used as input but also for a large number of additional configurations derived from ab initio molecular dynamics (AIMD) trajectories at finite temperature. Adiabatic molecular dynamics simulations on this PES reproduce the energy loss behavior of AIMD. EMT also provides expressions for the embedding electron density, which enabled us to develop a self-consistent approach to simulate nonadiabatic electron-hole pair excitation and their effect on the motion of the incident H-atoms. For H atoms with an energy of 2.7 eV colliding with Au, electron-hole pair excitation is by far the most important energy loss pathway, giving an average energy loss ≈3 times that of the adiabatic case. This increased energy loss enhances the probability of the H-atom remaining on or in the Au slab by a factor of 2. The most likely outcome for H-atoms that are not scattered also depends prodigiously on the energy transfer mechanism; for the nonadiabatic case, more than 50% of the H-atoms which do not scatter are adsorbed on the surface, while for the adiabatic case more than 50% pass entirely through the 4 layer simulation slab.

  16. X-ray Absorption Spectroscopy Characterization of Zn Underpotential Deposition on Au(111) from Phosphate Supporting Electrolyte

    SciTech Connect

    Lee, J R; O'Malley, R L; O'Connell, T J; Vollmer, A; Rayment, T

    2009-12-11

    Zn K-edge X-ray absorption spectroscopy (XAS) has been used to investigate the structure of Zn monolayers prepared on Au(111) electrodes via underpotential deposition (UPD) from phosphate supporting electrolyte. Theoretical modeling of the XAS data indicates that the Zn adatoms adopt a commensurate ({radical}3x{radical}3)R30{sup o} ({mu}{sub sc} = 0.33) adlayer structure and reside within the 3-fold hollow sites of the Au(111) surface. Meanwhile, phosphate counter-ions co-adsorb on the UPD adlayer and bridge between the Zn adatoms in a ({radical}3x{radical}3)R30{sup o} ({mu}{sub sc} = 0.33) configuration, with each phosphorous atom residing above a vacant 3-fold hollow site of the Au(111). Significantly, this surface structure is invariant between the electrochemical potential for UPD adlayer formation and the onset of bulk Zn electrodeposition. Analysis of the Zn K-edge absorption onset also presents the possibility that the Zn adatoms do not fully discharge during the process of UPD, which had been proposed in prior voltammetric studies of the phosphate/Zn(UPD)/Au(111) system.

  17. The structure, energetics, and nature of the chemical bonding of phenylthiol adsorbed on the Au(111) surface: implications for density-functional calculations of molecular-electronic conduction.

    PubMed

    Bilić, Ante; Reimers, Jeffrey R; Hush, Noel S

    2005-03-01

    The adsorption of phenylthiol on the Au(111) surface is modeled using Perdew and Wang density-functional calculations. Both direct molecular physisorption and dissociative chemisorption via S-H bond cleavage are considered as well as dimerization to form disulfides. For the major observed product, the chemisorbed thiol, an extensive potential-energy surface is produced as a function of both the azimuthal orientation of the adsorbate and the linear translation of the adsorbate through the key fcc, hcp, bridge, and top binding sites. Key structures are characterized, the lowest-energy one being a broad minimum of tilted orientation ranging from the bridge structure halfway towards the fcc one. The vertically oriented threefold binding sites, often assumed to dominate molecular electronics measurements, are identified as transition states at low coverage but become favored in dense monolayers. A similar surface is also produced for chemisorption of phenylthiol on Ag(111); this displays significant qualitative differences, consistent with the qualitatively different observed structures for thiol chemisorption on Ag and Au. Full contours of the minimum potential energy as a function of sulfur translation over the crystal face are described, from which the barrier to diffusion is deduced to be 5.8 kcal mol(-1), indicating that the potential-energy surface has low corrugation. The calculated bond lengths, adsorbate charge and spin density, and the density of electronic states all indicate that, at all sulfur locations, the adsorbate can be regarded as a thiyl species that forms a net single covalent bond to the surface of strength 31 kcal mol(-1). No detectable thiolate character is predicted, however, contrary to experimental results for alkyl thiols that indicate up to 20%-30% thiolate involvement. This effect is attributed to the asymptotic-potential error of all modern density functionals that becomes manifest through a 3-4 eV error in the lineup of the adsorbate and

  18. Vacuum synthesis of magnetic aluminum phthalocyanine on Au(111).

    PubMed

    Hong, I-Po; Li, Na; Zhang, Ya-Jie; Wang, Hao; Song, Huan-Jun; Bai, Mei-Lin; Zhou, Xiong; Li, Jian-Long; Gu, Gao-Chen; Zhang, Xue; Chen, Min; Gottfried, J Michael; Wang, Dong; Lü, Jing-Tao; Peng, Lian-Mao; Hou, Shi-Min; Berndt, Richard; Wu, Kai; Wang, Yong-Feng

    2016-08-16

    Air-unstable magnetic aluminum phthalocyanine (AlPc) molecules are prepared by an on-surface metalation reaction of phthalocyanine with aluminum (Al) atoms on Au(111) in ultrahigh vacuum. Experiments and density functional theory calculations show that an unpaired spin is located on the conjugated isoindole lobes of the molecule rather than at the Al position. PMID:27406881

  19. Surface morphologies, electronic structures, and Kondo effect of lanthanide(III)-phthalocyanine molecules on Au(111) by using STM, STS and FET properties for next generation devices.

    PubMed

    Katoh, Keiichi; Komeda, Tadahiro; Yamashita, Masahiro

    2010-05-28

    The crystal structures of double-decker single-molecule magnets (SMMs) LnPc(2) (Ln = Tb(III) and Dy(III); Pc = phthalocyanine) and non-SMM YPc(2) were determined by using single crystal X-ray diffraction analysis. The compounds are isomorphous to each other. The compounds have metal-centers (M(3+) = Tb, Dy, and Y) sandwiched by two Pc ligands via eight isoindole-nitrogen atoms in a square-antiprism fashion. The twist angle between the two Pc ligands is 41.4 degrees. Scanning tunneling microscopy (STM) was used to investigate the compounds adsorbed on a Au(111) surface, deposited by using thermal evaporation in ultra-high vacuum. Both MPc(2) with eight-lobes and MPc with four-lobes, which has lost one Pc ligand, were observed. In the scanning tunneling spectroscopy (STS) images of TbPc molecules at 4.8 K, a Kondo peak with a Kondo temperature (T(K)) of approximately 250 K was observed near the Fermi level (V = 0 V). On the other hand, DyPc, YPc and MPc(2) exhibited no Kondo peak. In order to understand the observed Kondo effect, the energy splitting of sublevels in a crystal field should be taken into consideration. As the next step in our studies on the SMM/Kondo effect in Tb-Pc derivatives, we investigated the electronic transport properties of Ln-Pc molecules as the active layer in top- and bottom-contact thin-film organic field effect transistor (OFETs) devices. Tb-Pc molecule devices exhibit p-type semiconducting properties with a hole mobility (mu(H)) of approximately 10(-4) cm(2) V(-1) s(-1). Interestingly, the Dy-Pc based devices exhibited ambipolar semiconducting properties with an electron mobility (mu(e)) of approximately 10(-5) and a hole mobility (mu(H)) of approximately 10(-4) cm(2) V(-1) s(-1). This behavior has important implications for the electronic structure of the molecules. PMID:20396817

  20. An in situ study of reconstructed gold electrode surfaces by second harmonic generation

    NASA Astrophysics Data System (ADS)

    Friedrich, A.; Pettinger, B.; Kolb, D. M.; Lüpke, G.; Steinhoff, R.; Marowsky, G.

    1989-11-01

    Second harmonic generation (SHG) was employed to monitor in situ the potential-induced reconstruction of Au(111) and Au(100) electrodes. Rotating the sample by 360° about the surface normal yields for the unreconstructed Au(111)-(1×1) surface the well-known threefold symmetry pattern in the SHG intensity, while Au(100)-(1×1) shows no rotational anisotropy, as expected for C 4v symmetry. For the reconstructed Au(111)-(1×23) surface, however, an additional onefold symmetry pattern is observed, which allows in situ monitoring of the structural transition between (1×1) and (1×23). For the reconstructed Au(100)-(5×20) surface, a threefold symmetry pattern was found.

  1. Enhancing the reactivity of gold: Nanostructured Au(111) adsorbs CO

    NASA Astrophysics Data System (ADS)

    Hoffmann, F. M.; Hrbek, J.; Ma, S.; Park, J. B.; Rodriguez, J. A.; Stacchiola, D. J.; Senanayake, S. D.

    2016-08-01

    Low-coordinated sites are surface defects whose presence can transform a surface of inert or noble metal such as Au into an active catalyst. Starting with a well-ordered Au(111) surface we prepared by ion sputtering gold surfaces modified by pits, used microscopy (STM) for their structural characterization and CO spectroscopy (IRAS and NEXAFS) for probing reactivity of surface defects. In contrast to the Au(111) surface CO adsorbs readily on the pitted surfaces bonding to low-coordinated sites identified as step atoms forming {111} and {100} microfacets. Pitted nanostructured surfaces can serve as interesting and easily prepared models of catalytic surfaces with defined defects that offer an attractive alternative to vicinal surfaces or nanoparticles commonly employed in catalysis science.

  2. Enhancing the reactivity of gold: Nanostructured Au(111) adsorbs CO

    DOE PAGES

    Hoffmann, F. M.; Hrbek, J.; Ma, S.; Park, J. B.; Rodriguez, J. A.; Stacchiola, D. J.; Senanayake, S. D.

    2015-12-02

    Low-coordinated sites are surface defects whose presence can transform a surface of inert or noble metal such as Au into an active catalyst. We prepared gold surfaces modified by pits, starting with a well-ordered Au(111) surface; we then used microscopy (STM) for their structural characterization and CO spectroscopy (IRAS and NEXAFS) for probing reactivity of surface defects. In contrast to the Au(111) surface CO adsorbs readily on the pitted surfaces bonding to low-coordinated sites identified as step atoms forming {111} and {100} microfacets. Finally, pitted nanostructured surfaces can serve as interesting and easily prepared models of catalytic surfaces with definedmore » defects that offer an attractive alternative to vicinal surfaces or nanoparticles commonly employed in catalysis science.« less

  3. Enhancing the reactivity of gold: Nanostructured Au(111) adsorbs CO

    SciTech Connect

    Hoffmann, F. M.; Hrbek, J.; Ma, S.; Park, J. B.; Rodriguez, J. A.; Stacchiola, D. J.; Senanayake, S. D.

    2015-12-02

    Low-coordinated sites are surface defects whose presence can transform a surface of inert or noble metal such as Au into an active catalyst. We prepared gold surfaces modified by pits, starting with a well-ordered Au(111) surface; we then used microscopy (STM) for their structural characterization and CO spectroscopy (IRAS and NEXAFS) for probing reactivity of surface defects. In contrast to the Au(111) surface CO adsorbs readily on the pitted surfaces bonding to low-coordinated sites identified as step atoms forming {111} and {100} microfacets. Finally, pitted nanostructured surfaces can serve as interesting and easily prepared models of catalytic surfaces with defined defects that offer an attractive alternative to vicinal surfaces or nanoparticles commonly employed in catalysis science.

  4. Activated Dissociation of HCl on Au(111).

    PubMed

    Shirhatti, Pranav R; Geweke, Jan; Steinsiek, Christoph; Bartels, Christof; Rahinov, Igor; Auerbach, Daniel J; Wodtke, Alec M

    2016-04-01

    We report zero-coverage reaction probabilities (S0) for HCl dissociative adsorption on Au(111) obtained by the seeded molecular beam hot-nozzle method. For measurements at normal incidence with mean translational energies ranging from 0.94 to 2.56 eV (nozzle temperatures 296 to 1060 K), S0 increased from 6 × 10(-6) to 2 × 10(-2). S0 also increased with increasing nozzle temperature for fixed incidence energy associated with the motion normal to the surface. Accounting for the influence of the vibrational state population and translational energy distributions in the incident beam, we are able to compare the experimental results to recent theoretical predictions. These calculations, performed employing 6-D quantum dynamics on an electronically adiabatic potential energy surface obtained using density functional theory at the level of the generalized gradient approximation and the static surface approximation, severely overestimate the reaction probabilities when compared with our experimental results. We discuss some possible reasons for this large disagreement. PMID:26990513

  5. In situ x-ray scattering studies of the Au(111)/electrolyte interface

    SciTech Connect

    Wang, Jia; Ocko, B.M.; Davenport, A.J.; Isaacs, H.S.

    1991-01-01

    The adsorption of anions at the Au(111) electrode and the subsequent effect on the gold surface structure have been investigated using x-ray specular reflectivity and grazing incident angle diffraction techniques. The top layer of gold atoms undergoes a reversible phase transition between the (1{times}1) bulk termination and a (23{times}{radical}{bar 3}) reconstructed phase on changing the potential. The shifts of the phase transition potential in NaCland NaBr solutions from the one in NaF can be understood by the anion adsorption induced charge effect. The reconstruction formation rate increases in chloride and bromide solutions due to an increase in the surface mobility with anion adsorption. Adsorbed chloride and bromide monolayers can be monitored during a potential scan by the specular reflectivity.

  6. In situ x-ray scattering studies of the Au(111)/electrolyte interface

    SciTech Connect

    Wang, Jia; Ocko, B.M.; Davenport, A.J.; Isaacs, H.S.

    1991-12-31

    The adsorption of anions at the Au(111) electrode and the subsequent effect on the gold surface structure have been investigated using x-ray specular reflectivity and grazing incident angle diffraction techniques. The top layer of gold atoms undergoes a reversible phase transition between the (1{times}1) bulk termination and a (23{times}{radical}{bar 3}) reconstructed phase on changing the potential. The shifts of the phase transition potential in NaCland NaBr solutions from the one in NaF can be understood by the anion adsorption induced charge effect. The reconstruction formation rate increases in chloride and bromide solutions due to an increase in the surface mobility with anion adsorption. Adsorbed chloride and bromide monolayers can be monitored during a potential scan by the specular reflectivity.

  7. Temperature programmed desorption of weakly bound adsorbates on Au(111)

    NASA Astrophysics Data System (ADS)

    Engelhart, Daniel P.; Wagner, Roman J. V.; Meling, Artur; Wodtke, Alec M.; Schäfer, Tim

    2016-08-01

    We have performed temperature programmed desorption (TPD) experiments to analyze the desorption kinetics of Ar, Kr, Xe, C2H2, SF6, N2, NO and CO on Au(111). We report desorption activation energies (Edes), which are an excellent proxy for the binding energies. The derived binding energies scale with the polarizability of the molecules, consistent with the conclusion that the surface-adsorbate bonds arise due to dispersion forces. The reported results serve as a benchmark for theories of dispersion force interactions of molecules at metal surfaces.

  8. Enzyme immobilisation on self-organised nanopatterned electrode surfaces.

    PubMed

    Gajdzik, Janine; Lenz, Jennifer; Natter, Harald; Hempelmann, Rolf; Kohring, Gert-Wieland; Giffhorn, Friedrich; Manolova, Mila; Kolb, Dieter M

    2010-10-21

    A new method is described for immobilisation of enzymes on polymer-coated Pt islands. These islands are deposited on top of a SAM-covered Au(111) electrode by a combination of electroless and electrochemical deposition, which allows for a variation of island size and distance between the islands. Here we describe the immobilisation of pyranose-2-oxidase (P2Ox) and the catalytic response to D-glucose on such a nanopatterned surface, which provides optimum access to the active centres of the enzyme.

  9. Adsorption and thermal decomposition of 2-octylthieno[3,4-b]thiophene on Au(111).

    PubMed

    Park, Joon B; Zong, Kyukwan; Jeon, Il Chul; Hahn, Jae Ryang; Stacchiola, Dario; Starr, David; Müller, Kathrin; Noh, Jaegeun

    2012-10-15

    The adsorption and thermal stability of 2-octylthieno[3,4-b]thiophene (OTTP) on the Au(111) surfaces have been studied using scanning tunneling microscopy (STM), temperature programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS). UHV-STM studies revealed that the vapor-deposited OTTP on Au(111) generated disordered adlayers with monolayer thickness even at saturation coverage. XPS and TPD studies indicated that OTTP molecules on Au(111) are stable up to 450 K and further heating of the sample resulted in thermal decomposition to produce H(2) and H(2)S via C-S bond scission in the thieno-thiophene rings. Dehydrogenation continues to occur above 600 K and the molecules were ultimately transformed to carbon clusters at 900 K. Highly resolved air-STM images showed that OTTP adlayers on Au(111) prepared from solution are composed of a well-ordered and low-coverage phase where the molecules lie flat on the surface, which can be assigned as a (9×2√33)R5° structure. Finally, based on analysis of STM, TPD, and XPS results, we propose a thermal decomposition mechanism of OTTP on Au(111) as a function of annealing temperature. PMID:22818203

  10. Photoemission core-level shifts reveal the thiolate-Au(111) interface

    SciTech Connect

    Groenbeck, Henrik; Odelius, Michael

    2010-08-15

    The nature of the thiolate/Au(111) interface is a long-standing puzzle. It has been suggested that thiolates drive surface reconstruction, however, a consensus regarding the adsorption configuration is missing. Herein, the density-functional theory is used to evaluate surface core-level shifts (SCLSs) for methyl thiolates on Au(111) assuming a representative set of different surface reconstructions. The SCLSs are found to provide sensitive fingerprints of the anchoring configuration, and it is only thiolate adsorption in the form of MeS-Au-SMe complexes that can be reconciled with experimental data.

  11. CO₂ electroreduction at bare and Cu-decorated Pd pseudomorphic layers: catalyst tuning by controlled and indirect supporting onto Au(111).

    PubMed

    Januszewska, Aneta; Jurczakowski, Rafal; Kulesza, Pawel J

    2014-12-01

    We report here the results of electrochemical studies on CO2 electroreduction at multilayered catalyst composed of the monatomic layer of copper covering palladium overlayers (0.8-10 monolayers) deposited on the well-defined Au(111) surface. These multilayered systems were obtained by successive underpotential deposition steps: Pd on Au(111) as well as Cu on Pd/Au(111). Low index orientation of Au substrate was chosen to compare Pd overlayers with bulk Pd(111), which is known to reduce CO2 to CO adsorbates in acidic solutions. The process of CO2 electroreduction was studied by using classical transient electrochemical methods. Catalytic activity of bare Pd layers was investigated in acidic and neutral solutions. In the latter case, much higher activity of Pd overlayers was observed. The results showed that the palladium layer thickness significantly changed the catalytic activities of both bare Pd overlayers and the one Cu monolayer covered electrodes toward CO2 electroreduction. Results show that catalytic activity can be finely tuned by using the multilayered near-surface-alloy approach. PMID:25350872

  12. Effects of protonation of pyridine moieties on the 2D assembly of porphyrin layers on Au(111) at electrochemical interfaces.

    PubMed

    Yoshimoto, Soichiro

    2012-05-14

    Unique molecular assemblies of a porphyrin derivative are prepared on Au(111) by controlling the protonation/unprotonation of the pyridine groups. The porphyrin derivative, driven by the protonation of the pyridine groups, can provide characteristic assemblies with specific molecular conformations on an Au(111) surface at the electrochemical interface. In situ scanning tunneling microscopy images revealed clear differences in the adlayer structures for the unprotonated and the protonated forms of the molecules that depended upon the electrochemical potential.

  13. Coverage Dependent Assembly of Anthraquinone on Au(111)

    NASA Astrophysics Data System (ADS)

    Conrad, Brad; Deloach, Andrew; Einstein, Theodore; Dougherty, Daniel

    A study of adsorbate-adsorbate and surface state mediated interactions of anthraquinone (AnQ) on Au(111) is presented. We utilize scanning tunneling microscopy (STM) to characterize the coverage dependence of AnQ structure formation. Ordered structures are observed up to a single monolayer (ML) and are found to be strongly dependent on molecular surface density. While the complete ML forms a well-ordered close-packed layer, for a narrow range of sub-ML coverages irregular close-packed islands are observed to coexist with a disordered pore network linking neighboring islands. This network displays a characteristic pore size and at lower coverages, the soliton walls of the herringbone reconstruction are shown to promote formation of distinct pore nanostructures. We will discuss these nanostructure formations in the context of surface mediated and more direct adsorbate interactions.

  14. Structure sensitive in situ Raman study of iron passive films using SERS-active Fe/Au(111) substrates

    NASA Astrophysics Data System (ADS)

    Allongue, P.; Joiret, S.

    2005-03-01

    This work describes the preparation of well-defined Fe/Au(111) /mica substrates for in situ Raman studies of the iron passive film with surface-enhanced Raman scattering (SERS). It is a two-step technique in which a SERS active (111) epitaxial gold substrate is prepared by resistive evaporation on mica. An epitaxial Fe(110) film is then electrodeposited to serve as iron electrode. It is shown that the SERS enhancement factor depends primarily on the good matching between the gold film plasmon resonance wavelength λP and the excitation wavelength. The iron thickness is the second main parameter controlling the SERS enhancement factor with a maximum found for a thickness of 20 monolayers. Under optimized conditions an amplification factor of 5×104 is demonstrated with respect to the case of a bulk polycrystalline iron substrate. This technique allows the recording of Raman spectra of nm-thick passive films within a few seconds only, which opens up to nearly real-time bias-dependent investigations of the chemistry at the electrochemical interface. In addition, taking advantage of the well-defined structure of the Fe(110)/Au(111)/ mica substrates, we present a preliminary structure-sensitive in situ Raman study of the iron passive film formed in a borate solution of pH8.4 . It is thought that this simple approach of promoting SERS should find more general interest for the electrochemistry community.

  15. Synthesis of ordered conjugated polycyclic aromatic hydrocarbon polymers through polymerization reaction on Au(111).

    PubMed

    Wang, Zhongping; Zhao, Huiling; Lu, Yan; Xiang, Feifei; Leng, Xinli; Liu, Xiaoqing; Song, Xin; Dong, Mingdong; Wang, Li

    2016-06-28

    One-dimensional π-conjugated polymer chains with variable lengths have been synthesized successfully via thermal polymerization reaction on the Au(111) surface. Such polymer chains form parallel arrays along specific directions according to the initial assembly orientations of the close-packed Br-BTTN precursors. PMID:27302478

  16. Chlorine adlayer-templated growth of a hybrid inorganic-organic layered structure on Au(111)

    NASA Astrophysics Data System (ADS)

    Rzeźnicka, I. I.; Horino, H.; Yagyu, K.; Suzuki, T.; Kajimoto, S.; Fukumura, H.

    2016-10-01

    Growth of a hybrid inorganic-organic layered structure on the Au(111) surface using a one-step solution growth is reported. The hybrid structure is consist of 4,4‧-bipyridine [4,4‧-BiPyH2]2 + cations, Cl anions and Au adatoms, provided from substrate by means of the adsorbate-induced surface phase transition of a surface reconstruction. Its surface and bulk structures were characterized by scanning tunneling microscopy (STM), secondary ion mass spectrometry (SIMS), and Raman spectroscopy. STM results reveal growth of the first [4,4‧-BiPyH2]2 + layer on top of the p(√{ 3} ×√{ 3})" separators=", R 30 ° chlorine overlayer formed on the Au(111) surface. These two layers are found to provide a platform for a following three-dimensional growth facilitated by hydrogen bonding, aurophilic and π-π stacking interactions.

  17. STM studies of the self-assembly of manganese porphyrin catalysts at the Au(111)-n-tetradecane interface

    NASA Astrophysics Data System (ADS)

    Hulsken, Bas; Elemans, Johannes A. A. W.; Gerritsen, Jan W.; Khoury, Tony; Crossley, Maxwell J.; Rowan, Alan E.; Nolte, Roeland J. M.; Speller, Sylvia

    2009-08-01

    The precise structure of monolayers of catalytic manganese porphyrins at the interface of an Au(111)-surface and an n-tetradecane liquid has been determined in a liquid-cell scanning tunneling microscope (STM). Before the addition of the manganese porphyrins, an ordered monolayer of lamellae of n-tetradecane molecules on the Au(111) surface could be imaged. It was found that only domain boundaries in this monolayer were correlated to the underlying gold surface, but not the orientation of the n-tetradecane lamellae and the molecules within them. Both the reconstruction of the Au(111) surface and the ordering of the first layer of n-tetradecane can direct the ordering of the manganese porphyrins that are subsequently added to the liquid phase.

  18. Intramolecularly resolved Kondo resonance of high-spin Fe (II ) -porphyrin adsorbed on Au ( 111 )

    NASA Astrophysics Data System (ADS)

    Wang, Weihua; Pang, Rui; Kuang, Guowen; Shi, Xingqiang; Shang, Xuesong; Liu, Pei Nian; Lin, Nian

    2015-01-01

    Using cryogenic scanning tunneling microscopy, we measured the electronic states and Kondo resonance of single Fe (II ) -porphyrin molecules adsorbed on a Au ( 111 ) surface with intramolecular resolution. We found that the Fe (II ) ion introduces a spin-polarized molecular state near the Fermi level. Tunneling spectroscopy revealed that this state gives rise to Kondo resonance exhibiting characteristics different from those of the Fe (II ) spin state. Spin-polarized density functional theory calculations revealed that the molecule was weakly adsorbed on the surface, yet still switches its spin configuration from S =1 to2 . The spin switching was found to be driven by three effects: a structural distortion of the macrocyclic ring from planar to saddle shaped, a weak chemical bonding between the Fe and the Au surface atom underneath, and weakened Fe-N bonds due to Au ( 111 ) -molecule charge transfer.

  19. Pit Formation during the Self-Assembly of Dithiol Monolayers on Au(111)

    NASA Astrophysics Data System (ADS)

    Macdairmid, A. R.; Cappello, M. L.; Keeler, W. J.; Banks, J. T.; Gallagher, M. C.

    2000-03-01

    The formation of pits one gold atom deep during the growth of alkanethiol monolayers on Au(111), has been observed previously by others. Explanations for pit formation include etching of the substrate, or mass transport of gold atom + thiol molecule on the surface, due to changes in surface energy^1. We have investigated the structure of dithiothreitol (DTT) SAMs on Au(111). Ex situ STM measurements indicate similar pitting occurs during formation of the dithiol monolayer. The degree of pitting depends on exposure time, sample temperature during formation, and subsequent annealing of the sample. Pitting is enhanced considerasbly when DTT is coordinated with Ti, in fact DTT/Ti films exhibit considerable pit motion during STM imaging. ^1 F. Teran et al. Electrochimica Acta 44, 1053 (1998).

  20. Extraordinary epitaxial alignment of graphene islands on Au(111)

    NASA Astrophysics Data System (ADS)

    Wofford, Joseph M.; Starodub, Elena; Walter, Andrew L.; Nie, Shu; Bostwick, Aaron; Bartelt, Norman C.; Thürmer, Konrad; Rotenberg, Eli; McCarty, Kevin F.; Dubon, Oscar D.

    2012-05-01

    Pristine, single-crystalline graphene displays a unique collection of remarkable electronic properties that arise from its two-dimensional, honeycomb structure. Using in situ low-energy electron microscopy, we show that when deposited on the (111) surface of Au carbon forms such a structure. The resulting monolayer, epitaxial film is formed by the coalescence of dendritic graphene islands that nucleate at a high density. Over 95% of these islands can be identically aligned with respect to each other and to the Au substrate. Remarkably, the dominant island orientation is not the better lattice-matched 30° rotated orientation but instead one in which the graphene [01] and Au [011] in-plane directions are parallel. The epitaxial graphene film is only weakly coupled to the Au surface, which maintains its reconstruction under the slightly p-type doped graphene. The linear electronic dispersion characteristic of free-standing graphene is retained regardless of orientation. That a weakly interacting, non-lattice matched substrate is able to lock graphene into a particular orientation is surprising. This ability, however, makes Au(111) a promising substrate for the growth of single crystalline graphene films.

  1. Structural and electronic properties of graphene nanoflakes on Au(111) and Ag(111)

    PubMed Central

    Tesch, Julia; Leicht, Philipp; Blumenschein, Felix; Gragnaniello, Luca; Fonin, Mikhail; Marsoner Steinkasserer, Lukas Eugen; Paulus, Beate; Voloshina, Elena; Dedkov, Yuriy

    2016-01-01

    We investigate the electronic properties of graphene nanoflakes on Ag(111) and Au(111) surfaces by means of scanning tunneling microscopy and spectroscopy as well as density functional theory calculations. Quasiparticle interference mapping allows for the clear distinction of substrate-derived contributions in scattering and those originating from graphene nanoflakes. Our analysis shows that the parabolic dispersion of Au(111) and Ag(111) surface states remains unchanged with the band minimum shifted to higher energies for the regions of the metal surface covered by graphene, reflecting a rather weak interaction between graphene and the metal surface. The analysis of graphene-related scattering on single nanoflakes yields a linear dispersion relation E(k), with a slight p-doping for graphene/Au(111) and a larger n-doping for graphene/Ag(111). The obtained experimental data (doping level, band dispersions around EF, and Fermi velocity) are very well reproduced within DFT-D2/D3 approaches, which provide a detailed insight into the site-specific interaction between graphene and the underlying substrate. PMID:27002297

  2. From porphyrins to pyrphyrins: adsorption study and metalation of a molecular catalyst on Au(111).

    PubMed

    Mette, Gerson; Sutter, Denys; Gurdal, Yeliz; Schnidrig, Stephan; Probst, Benjamin; Iannuzzi, Marcella; Hutter, Jürg; Alberto, Roger; Osterwalder, Jürg

    2016-04-21

    The molecular ligand pyrphyrin, a tetradentate bipyridine based macrocycle, represents an interesting but widely unexplored class of molecules. It resembles the well-known porphyrin, but consists of pyridyl subunits instead of pyrroles. Metal complexes based on pyrphyrin ligands have recently shown promise as water reduction catalysts in homogeneous photochemical water splitting reactions. In this study, the adsorption and metalation of pyrphyrin on a single crystalline Au(111) surface is investigated in an ultrahigh vacuum by means of scanning tunneling microscopy, low-energy electron diffraction, X-ray photoelectron spectroscopy and density functional theory. Pyrphyrin coverages of approximately one monolayer and less are obtained by sublimation of the molecules on the substrate kept at room temperature. The molecules self-assemble in two distinct phases of long-range molecular ordering depending on the surface coverage. The deposition of cobalt metal and subsequent annealing lead to the formation of Co-ligated pyrphyrin molecules accompanied by a pronounced change of the molecular self-assembly. Electronic structure calculations taking the herringbone reconstruction of Au(111) into account show that the molecules are physisorbed, but preferred adsorption sites are identified where Co and the N atoms of the two terminal cyano groups are optimally coordinated to the surface Au atoms. An intermediate state of the metalation reaction is observed and the reaction steps for the Co metalation of pyrphyrin molecules on Au(111) are established in a joint experimental and computational effort. PMID:27006307

  3. Magnetic and electronic structure of Mn nanostructures on Ag(111) and Au(111)

    NASA Astrophysics Data System (ADS)

    Cardias, R.; Bezerra-Neto, M. M.; Ribeiro, M. S.; Bergman, A.; Szilva, A.; Eriksson, O.; Klautau, A. B.

    2016-01-01

    We present results of the electronic and magnetic structure of Mn nanowires adsorbed on Ag(111) and Au(111) surfaces. For finite Mn nanowires on Ag(111) and Au(111) surfaces, our ab initio results show that the large difference between the spin-orbit splitting of these two surfaces leads to completely different magnetic configurations. The magnetic ordering for Mn nanowires adsorbed on Ag(111) is governed by the strong exchange interaction between Mn adatoms. For Mn nano-chains on Au(111), the competition between Heisenberg and Dzyaloshinskii-Moriya interactions leads to a complex magnetic structure of the clusters considered here. Among the more conspicuous results we note a spin-spiral helical type for the nanowire with seven atoms, and a complex magnetic configuration incommensurate with the substrate lattice for a double-sized Mn wire. The effect of the structural relaxation is also investigated, showing sensitivity of the exchange interactions to the bond distance to the substrate. We also demonstrate that small changes in the band filling of these Mn chains results in drastically different changes of the interatomic exchange. Finally, we show that dispersion of the electronic energy spectrum is possible even in nanostructures with bounded spatial extension.

  4. Formation of Ordered 4-Fluorobenzenethiol Self-Assembled Monolayers on Au(111) from Vapor Phase Deposition.

    PubMed

    Kang, Hungu; Ito, Eisuke; Hara, Masahiko; Noh, Jaegeun

    2016-03-01

    Self-assembled monolayers (SAMs) were formed by the spontaneous adsorption of 4-fluorobenzenethiol (4-FBT) on Au(111) using both solution and ambient-pressure vapor deposition methods at room temperature. The surface structure and thermal desorption properties of 4-FBT SAMs were examined by scanning tunneling microscopy (STM) and thermal desorption spectroscopy (TDS). STM imaging showed that 4-FBT SAMs formed in solution at room temperature mainly contained disordered phase with gold adatom islands, while those formed by ambient-pressure vapor deposition had well-ordered phase, which can be described as a (2 x 2√13)R45 degrees structure. In addition, thermal desorption spectroscopy (TDS) measurements showed that strong desorption peak for parent mass fragment (m/z = 128, FC6H5SH+) for 4-FBT SAMs on Au(111) was observed at 460 K, as a result of hydrogen abstract reaction of chemisorbed thiolates during desorption. PMID:27455712

  5. Light-induced reversible modification of the work function of a new perfluorinated biphenyl azobenzene chemisorbed on Au (111)

    NASA Astrophysics Data System (ADS)

    Masillamani, Appan Merari; Osella, Silvio; Liscio, Andrea; Fenwick, Oliver; Reinders, Federica; Mayor, Marcel; Palermo, Vincenzo; Cornil, Jérôme; Samorì, Paolo

    2014-07-01

    We describe the synthesis of a novel biphenyl azobenzene derivative exhibiting: (i) a protected thiol anchoring group in the α-position to readily form self-assembled monolayers (SAMs) on Au surfaces; and (ii) a terminal perfluorinated benzene ring in the ω-position to modify the surface properties. The design of this molecule ensured both an efficient in situ photoswitching between the trans and cis isomers when chemisorbed on Au(111), due to the presence of a biphenyl bridge between the thiol protected anchoring group and the azo dye, and a significant variation of the work function of the SAM in the two isomeric states, induced by the perfluorinated phenyl head group. By exploiting the light responsive nature of the chemisorbed molecules, it is possible to dynamically modify in situ the work function of the SAM-covered electrode, as demonstrated both experimentally and by quantum-chemical calculations, revealing changes in work function up to 220 meV. These findings are relevant for tuning the work function of metallic electrodes, and hence to dynamically modulate charge injection at metal-semiconductor interfaces for organic opto-electronic applications.We describe the synthesis of a novel biphenyl azobenzene derivative exhibiting: (i) a protected thiol anchoring group in the α-position to readily form self-assembled monolayers (SAMs) on Au surfaces; and (ii) a terminal perfluorinated benzene ring in the ω-position to modify the surface properties. The design of this molecule ensured both an efficient in situ photoswitching between the trans and cis isomers when chemisorbed on Au(111), due to the presence of a biphenyl bridge between the thiol protected anchoring group and the azo dye, and a significant variation of the work function of the SAM in the two isomeric states, induced by the perfluorinated phenyl head group. By exploiting the light responsive nature of the chemisorbed molecules, it is possible to dynamically modify in situ the work function of

  6. Kinetics of low-temperature CO oxidation on Au(111)

    NASA Astrophysics Data System (ADS)

    Thuening, Theodore; Walker, Joshua; Adams, Heather; Furlong, Octavio; Tysoe, Wilfred T.

    2016-06-01

    The oxidation of carbon monoxide on oxygen-modified Au(111) surfaces is studied using a combination of reflection-absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD). TPD reveals that CO desorbs in two states with the low-temperature state have a peak temperature between ~ 130 and 150 K, and the higher-temperature state having a peak temperature that varies from ~ 175 to ~ 220 K depending on the initial oxygen and CO coverages. Infrared spectroscopy indicates that the low-temperature CO desorption state is predominantly associated with CO adsorbed on Auδ + sites, while the higher-temperature states are due to CO on Au0 sites. No additional vibrational features are detected indicating that CO reacts directly with adsorbed atomic oxygen on gold to form CO2. Estimates of the activation energy for CO2 formation suggest that they are in the same range and found for supported gold catalysts at reaction temperature below ~ 300 K.

  7. Substrate-controlled linking of molecular building blocks: Au(111) vs. Cu(111)

    NASA Astrophysics Data System (ADS)

    Koch, Matthias; Gille, Marie; Viertel, Andreas; Hecht, Stefan; Grill, Leonhard

    2014-09-01

    The coupling of dibromohexabenzocoronene (Br2-HBC) as a precursor molecule is investigated by scanning tunneling microscopy (STM) on two noble metal surfaces: Au(111) and Cu(111). It is found that the on-surface polymerization of molecular building blocks equipped with halogen atoms is strongly influenced by the choice of the substrate. While on Au(111) a heating step of up to 520 K is required to activate the molecules and form polymers, on Cu(111) the catalytic reactivity causes activation already below room temperature. Due to the different substrates, the intramolecular bonds in the polymers between the HBC units differ: The HBC molecules are covalently coupled on Au(111) while on Cu(111) a copper adatom mediates the bonding. This effect is proven by the comparison with gas phase calculations and by lateral manipulation with the STM tip. The choice of the substrate thus does not only define the activation temperature but also lead to different bonding strengths between the molecular building blocks.

  8. Interaction of CO with OH on Au(111): HCOO, CO3, and HOCO as Key Intermediates in the Water-Gas Shift Reaction

    SciTech Connect

    Senanayake, S.; Stacchiola, D; Liu, P; Mullins, C; Hrbek, J; Rodriguez, J

    2009-01-01

    We have investigated the role of formate (HCOO), carbonate (CO{sub 3}), and carboxyl (HOCO) species as possible intermediates in the OH{sub ads} + CO{sub gas} {yields} CO{sub 2,gas} + 0.5H{sub 2,gas} reaction on Au(111) using synchrotron-based core level photoemission, near-edge X-ray absorption fine structure (NEXAFS), and infrared absorption spectroscopy (IR). Adsorbed HCOO, CO{sub 3}, and OH species were prepared by adsorbing formic acid, carbon dioxide, and water on a Au(111) surface precovered with 0.2 ML of atomic oxygen, respectively. HCOOH interacts weakly with Au(111), but on O/Au(111) it dissociates its acidic H to yield adsorbed formate. The results of NEXAFS, IR, and density-functional calculations indicate that the formate adopts a bidentate configuration on Au(111). Since the HCOO groups are stable on Au(111) up to temperatures near 350 K, it is not likely that formate is a key intermediate for the OH{sub ads} + CO{sub gas} {yields} CO{sub 2,gas} + 0.5H{sub 2,gas} reaction at low temperatures. In fact, the formation of this species could lead eventually to surface poisoning. When compared to a formate species, a carbonate species formed by the reaction of CO{sub 2} with O/Au(111) has low stability, decomposing at temperatures between 100 and 125 K, and should not poison the gold surface. Neither HCOO nor CO{sub 3} was detected during the reaction of CO with OH on Au(111) at 90-120 K. The results of photoemission and IR spectroscopy point to HO {leftrightarrow} CO interactions, consistent with the formation of an unstable HOCO intermediate which has a very short lifetime on the gold surface. The possible mechanism for the low-temperature water-gas shift on gold catalysts is discussed in light of these results.

  9. Direct observation of adsorption geometry for the van der Waals adsorption of a single π-conjugated hydrocarbon molecule on Au(111)

    SciTech Connect

    Kim, Ju-Hyung; Jung, Jaehoon; Kim, Yousoo E-mail: ykim@riken.jp; Tahara, Kazukuni; Tobe, Yoshito E-mail: ykim@riken.jp; Kawai, Maki E-mail: ykim@riken.jp

    2014-02-21

    Weak van der Waals adsorption of π-conjugated hydrocarbon molecules onto the gold surface, Au(111), is one of the essential processes in constructing organic-metal interfaces in organic electronics. Here we provide a first direct observation of adsorption geometry of a single π-conjugated hydrocarbon molecule on Au(111) using an atomically resolved scanning tunneling microscopy study combined with van der Waals density functional methodology. For the purpose, we utilized a highly symmetric π-conjugated hydrocarbon molecule, dehydrobenzo[12]annulene (DBA), which has a definite three-fold symmetry, the same as the Au(111) surface. Interestingly, our observations on an atomically resolved scale clearly indicate that the DBA molecule has only one adsorption configuration on Au(111) in spite of the weak van der Waals adsorption system. Based on the precisely determined adsorption geometry of DBA/Au(111), our calculation results imply that even a very small contribution of the interfacial orbital interaction at the organic-metal interface can play a decisive role in constraining the adsorption geometry even in the van der Waals adsorption system of a π-conjugated hydrocarbon molecule on the noblest Au(111) surface. Our observations provide not only deeper insight into the weak adsorption process, but also new perspectives to organic electronics using π-conjugated hydrocarbon molecules on the Au surface.

  10. Light-induced reversible modification of the work function of a new perfluorinated biphenyl azobenzene chemisorbed on Au (111).

    PubMed

    Masillamani, Appan Merari; Osella, Silvio; Liscio, Andrea; Fenwick, Oliver; Reinders, Federica; Mayor, Marcel; Palermo, Vincenzo; Cornil, Jérôme; Samorì, Paolo

    2014-08-01

    We describe the synthesis of a novel biphenyl azobenzene derivative exhibiting: (i) a protected thiol anchoring group in the α-position to readily form self-assembled monolayers (SAMs) on Au surfaces; and (ii) a terminal perfluorinated benzene ring in the ω-position to modify the surface properties. The design of this molecule ensured both an efficient in situ photoswitching between the trans and cis isomers when chemisorbed on Au(111), due to the presence of a biphenyl bridge between the thiol protected anchoring group and the azo dye, and a significant variation of the work function of the SAM in the two isomeric states, induced by the perfluorinated phenyl head group. By exploiting the light responsive nature of the chemisorbed molecules, it is possible to dynamically modify in situ the work function of the SAM-covered electrode, as demonstrated both experimentally and by quantum-chemical calculations, revealing changes in work function up to 220 meV. These findings are relevant for tuning the work function of metallic electrodes, and hence to dynamically modulate charge injection at metal-semiconductor interfaces for organic opto-electronic applications.

  11. From porphyrins to pyrphyrins: adsorption study and metalation of a molecular catalyst on Au(111)

    NASA Astrophysics Data System (ADS)

    Mette, Gerson; Sutter, Denys; Gurdal, Yeliz; Schnidrig, Stephan; Probst, Benjamin; Iannuzzi, Marcella; Hutter, Jürg; Alberto, Roger; Osterwalder, Jürg

    2016-04-01

    The molecular ligand pyrphyrin, a tetradentate bipyridine based macrocycle, represents an interesting but widely unexplored class of molecules. It resembles the well-known porphyrin, but consists of pyridyl subunits instead of pyrroles. Metal complexes based on pyrphyrin ligands have recently shown promise as water reduction catalysts in homogeneous photochemical water splitting reactions. In this study, the adsorption and metalation of pyrphyrin on a single crystalline Au(111) surface is investigated in an ultrahigh vacuum by means of scanning tunneling microscopy, low-energy electron diffraction, X-ray photoelectron spectroscopy and density functional theory. Pyrphyrin coverages of approximately one monolayer and less are obtained by sublimation of the molecules on the substrate kept at room temperature. The molecules self-assemble in two distinct phases of long-range molecular ordering depending on the surface coverage. The deposition of cobalt metal and subsequent annealing lead to the formation of Co-ligated pyrphyrin molecules accompanied by a pronounced change of the molecular self-assembly. Electronic structure calculations taking the herringbone reconstruction of Au(111) into account show that the molecules are physisorbed, but preferred adsorption sites are identified where Co and the N atoms of the two terminal cyano groups are optimally coordinated to the surface Au atoms. An intermediate state of the metalation reaction is observed and the reaction steps for the Co metalation of pyrphyrin molecules on Au(111) are established in a joint experimental and computational effort.The molecular ligand pyrphyrin, a tetradentate bipyridine based macrocycle, represents an interesting but widely unexplored class of molecules. It resembles the well-known porphyrin, but consists of pyridyl subunits instead of pyrroles. Metal complexes based on pyrphyrin ligands have recently shown promise as water reduction catalysts in homogeneous photochemical water splitting

  12. Structure and dynamics of C60 molecules on Au(111)

    SciTech Connect

    Shin, Heekeun; Schwarze, A; Diehl, R D; Pussi, K; Colombier, A; Gaudry, E.; Ledieu, J; McGuirk, G M; Serkovic Loli, L N; Fournee, V; Wang, Lin-Lin; Schull, G; Berndt, R

    2014-06-01

    Earlier studies of C60 adsorption on Au(111) reported many interesting and complex features. We have performed coordinated low-energy electron diffraction, scanning tunneling microscopy (STM), and density functional theory studies to elucidate some of the details of the monolayer commensurate (2√3 × 2√3)R30° phase. We have identified the adsorption geometries of the two states that image as dim and bright in STM. These consist of a C60 molecule with a hexagon side down in a vacancy (hex-vac) and a C60 molecule with a carbon-carbon 6:6 bond down on a top site (6:6-top), respectively. We have studied the detailed geometries of these states and find that there is little distortion of the C60 molecules, but there is a rearrangement of the substrate near the C60 molecules. The two types of molecules differ in height, by about 0.7 Å, which accounts for most of the difference in their contrast in the STM images. The monolayer displays dynamical behavior, in which the molecules flip from bright to dim, and vice versa. We interpret this flipping as the result of the diffusion of vacancies in the surface layers of the substrate. Our measurements of the dynamics of this flipping from one state to the other indicate that the activation energy is 0.66 ± 0.03 eV for flips that involve nearest-neighbor C60 molecules, and 0.93 ± 0.03 for more distant flips. Based on calculated activation energies for vacancies diffusing in Au, we interpret these to be a result of surface vacancy diffusion and bulk vacancy diffusion. These results are compared to the similar system of Ag(111)-(2√3 × 2√3)R30°-C60. In both systems, the formation of the commensurate C60 monolayer produces a large number of vacancies in the top substrate layer that are highly mobile, effectively melting the interfacial metal layer at temperatures well below their normal melting temperatures.

  13. Growth of nanocrystalline MoO3 on Au(111) studied by in-situ STM

    SciTech Connect

    Biener, M M; Biener, J; Schalek, R; Friend, C M

    2004-04-22

    The growth of nanocrystalline MoO{sub 3} islands on Au(111) using physical vapor deposition of Mo has been studied by scanning tunneling microscopy (STM) and low energy electron diffraction (LEED). The growth conditions affect the shape and distribution of the MoO{sub 3} nanostructures, providing a means of preparing materials with different percentages of edge sites that may have different chemical and physical properties than atoms in the interior of the nanostructures. MoO{sub 3} islands were prepared by physical vapor deposition of Mo and subsequent oxidation by NO{sub 2}exposure at temperatures between 450 K and 600 K. They exhibit a crystalline structure with a c(4x2) periodicity relative to unreconstructed Au(111). While the atomic-scale structure is identical to that of MoO{sub 3} islands prepared by chemical vapor deposition, we demonstrate that the distribution of MoO{sub 3} islands on the Au(111) surface reflects the distribution of Mo clusters prior to oxidation although the growth of MoO{sub 3} involves long-range mass transport via volatile MoO{sub 3} precursor species. The island morphology is kinetically controlled at 450 K, whereas an equilibrium shape is approached at higher preparation temperatures or after prolonged annealing at the elevated temperature. Mo deposition at or above 525 K leads to the formation of a Mo-Au surface alloy as indicated by the observation of embedded MoO{sub 3} islands after oxidation by NO{sub 2}. Au vacancy islands, formed when Mo and Au dealloy to produce vacancies, are observed for these growth conditions.

  14. Chiral effects in amino acid adsorption on Au(111): A comparison of cysteine, homocysteine and methionine

    NASA Astrophysics Data System (ADS)

    Popa, Tatiana; Ting, Elvis C. M.; Paci, Irina

    2014-11-01

    A combined classical/quantum methodology is used to examine chiral effects upon adsorption of three sulfur-containing amino acids on the Au(111) surface: cysteine, homocysteine and methionine. Parallel tempering Monte Carlo simulations were employed to broadly examine the configurational space of monomers, dimers and trimers of the molecules on the gold surface. Density functional theory was applied to promising structural targets in order to incorporate higher order electronic structure effects in a study of relative stabilities of the various molecular states upon adsorption. As the precursors of chiral structure formation, like and unlike dimers were investigated at some length, with consideration given to the mode of sorption (chemisorption of physisorption) and the existence of zwitterionic states. We found that neutral (non-zwitterionic) molecules adsorbed weakly on the highly-coordinated Au(111) surfaces. As a consequence, pair configurations in dimers were insufficiently constrained to lead to differential stabilities of homochiral and heterochiral dimers. Whereas neutral molecule interactions were non-discriminating, strong chiral discrimination was found in zwitterionic amino acids. The zwitterionic forms of the larger molecules equilibrated closer to the surface, and the stronger molecule-molecule and molecule-surface interactions were such that homochiral dimers were stable whereas heterochiral dimers were not.

  15. Adlayer structures of anthracenthiol on Au(111) after removal of covering multilayers with probe scan

    NASA Astrophysics Data System (ADS)

    Azzam, Waleed

    2016-05-01

    Self-assembled monolayers (SAMs) of anthracene-2-thiol (AnT) on Au(111) have been investigated using scanning tunneling microscopy (STM). A preparation of AnT-SAMs from ethanolic solutions results in a deposition of multilayer films. As a result, the general features that have been frequently observed for different systems of thiol-modified gold surfaces are hidden in AnT-SAMs. The thin overlayers on top of the chemisorbed anthracenethiolate monolayer are removed by the STM-tip after a repetitive scanning over the same part of the SAM at nondestructive imaging conditions. After ∼2 h of consecutive and continuous STM scanning, smooth AnT-SAM surfaces were formed. The polished surfaces contain vacancy depressions rather than the elevated gold islands which are typically formed after the adsorption of purely aromatic thiols such as AnT on Au(111). The STM data showed the coexistence of two distinct stable commensurate phases, namely, α and β. High-resolution STM images revealed a (√{ 3 } × 8) structure for the α phase and a (√{ 7 } × 4) R11° structure for the β phase whose unit cells contain, respectively, four and two molecules. The β phase was found to be 50% less densely packed than the α phase. The lower molecular density of the β phase should be correlated with a significantly larger tilt angle of the AnT molecular backbone with respect to the surface normal.

  16. Barrier height formation in organic blends/metal interfaces: Case of tetrathiafulvalene-tetracyanoquinodimethane/Au(111)

    SciTech Connect

    Martínez, José I.; Abad, Enrique; Beltrán, Juan I.; Flores, Fernando; Ortega, José

    2013-12-07

    The interface between the tetrathiafulvalene/tetracyanoquinodimethane (TTF-TCNQ) organic blend and the Au(111) metal surface is analyzed by Density Functional Theory calculations, including the effect of the charging energies on the molecule transport gaps. Given the strong donor and acceptor characters of the TTF and TCNQ molecules, respectively, there is a strong intermolecular interaction, with a relatively high charge transfer between the two organic materials, and between the organic layer and the metal surface. We find that the TCNQ LUMO peak is very close to the Fermi level; due to the interaction with the metal surface, the organic molecular levels are broadened, creating an important induced density of interface states (IDIS). We show that the interface energy level alignment is controlled by the charge transfer between TTF, TCNQ, and Au, and by the molecular dipoles created in the molecules because of their deformations when adsorbed on Au(111). A generalization of the Unified-IDIS model, to explain how the interface energy levels alignment is achieved for the case of this blended donor/acceptor organic layer, is presented by introducing matrix equations associated with the Charge Neutrality Levels of both organic materials and with their intermixed screening properties.

  17. Self-organization of S adatoms on Au(111): √3R30° rows at low coverage

    SciTech Connect

    Walen, Holly; Liu, Da-Jiang; Oh, Junepyo; Lim, Hyunseob; Kim, Yousoo; Evans, J. W.; Thiel, P. A.

    2015-07-07

    Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed clean surface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30° from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, derived using a limited cluster expansion based on density functional theory energetics. Models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures.

  18. Collective effects in physisorbed molecular hydrogen on Ni /Au (111 )

    NASA Astrophysics Data System (ADS)

    Therrien, A. J.; Pronschinske, A.; Murphy, C. J.; Lewis, E. A.; Liriano, M. L.; Marcinkowski, M. D.; Sykes, E. C. H.

    2015-10-01

    We report a system in which the rotational, vibrational, electronic, and structural properties of condensed molecular H2 can be measured with subnanometer precision using scanning tunneling microscopy. H2 physisorbs around Ni nanoparticles on Au (111 ) and displays many nonclassical characteristics, including unique disappearance upon heating that is due to changes in the time-averaged phonon ground state population. This collective phenomenon also gives rise to the appearance of submolecular features and constructive overlap at points where neighboring H2 ensembles meet. A model based on the spatial distribution of collective excitations is proposed to explain these properties.

  19. Growth of Single- and Bilayer ZnO on Au(111) and Interaction with Copper

    SciTech Connect

    Deng, Xingyi; Yao, Kun; Sun, Keju; Li, Wei-Xue; Lee, Junseok; Matranga, Christopher

    2013-05-02

    The stoichiometric single- and bi-layer ZnO(0001) have been prepared by reactive deposition of Zn on Au(111) and studied in detail with X-ray photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory calculations. Both single- and bi-layer ZnO(0001) adopt a planar, graphite-like structure similar to freestanding ZnO(0001) due to the weak van der Waals interactions dominating their adhesion with the Au(111) substrate. At higher temperature, the single-layer ZnO(0001) converts gradually to bi-layer ZnO(0001) due to the twice stronger interaction between two ZnO layers than the interfacial adhesion of ZnO with Au substrate. It is found that Cu atoms on the surface of bi-layer ZnO(0001) are mobile with a diffusion barrier of 0.31 eV, and likely to agglomerate and form nanosized particles at low coverages; while Cu atoms tend to penetrate a single layer of ZnO(0001) with a barrier of 0.10 eV, resulting in a Cu free surface.

  20. Sulfidization of Au(111) from thioacetic acid: an experimental and theoretical study.

    PubMed

    Fischer, Jeison A; Zoldan, Vinícius C; Benitez, Guillermo; Rubert, Aldo A; Ramirez, Eduardo A; Carro, Pilar; Salvarezza, Roberto C; Pasa, André A; Vela, Maria E

    2012-10-30

    We have studied the adsorption of thioacetic acid (TAAH) on Au(111) from solution deposition. The close proximity of the SH groups to CO groups makes this molecule very attractive for exploring the effect of the functional group on the stability of the S-C and S-Au bonds. Although thioacetic acid was supposed to decompose slowly in water by hydrolysis supplying hydrogen sulfide, this behavior is not expected in nonpolar solvents such as toluene or hexane. Therefore, we have used these solvents for TAAH self-assembly on the Au(111) surface. The characterization of the adsorbates has been done by electrochemical techniques, X-ray photoelectron spectroscopy (XPS), and scanning tunneling microscopy (STM). We have found that even in nonpolar solvents thioacetic acid decomposes to S. The results have been discussed on the basis that the adsorbed species suffer a cleavage on the Au surface, leaving the S attached to it. The dissociation is a spontaneous process that reaches the final state very fast once it is energetically favorable, as can be interpreted from DFT calculations. The thioacetic acid adsorption reveals the strong effect that produces a functional group and the key role of the S-H bond cleavage in the self-assembly process. PMID:23002810

  1. Self-organization of S adatoms on Au(111): √3R30° rows at low coverage

    DOE PAGES

    Walen, Holly; Liu, Da -Jiang; Oh, Junepyo; Lim, Hyunseob; Evans, J. W.; Kim, Yousoo; Thiel, P. A.

    2015-07-06

    Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed cleansurface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30° from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, we derivedmore » using a limited cluster expansion based on density functional theory energetics. Furthermore, models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures.« less

  2. Self-organization of S adatoms on Au(111): √3R30° rows at low coverage

    SciTech Connect

    Walen, Holly; Liu, Da -Jiang; Oh, Junepyo; Lim, Hyunseob; Evans, J. W.; Kim, Yousoo; Thiel, P. A.

    2015-07-06

    Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed cleansurface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30° from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, we derived using a limited cluster expansion based on density functional theory energetics. Furthermore, models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures.

  3. Oxidation of palladium on Au(111) and ZnO(0001) supports

    DOE PAGES

    Lallo, J.; Tenney, S. A.; Kramer, A.; Sutter, P.; Batzill, M.

    2014-10-21

    The oxidation of supported Pd-deposits on Au(111) and ZnO(0001) single crystals has been studied by x- ray photoemission spectroscopy (XPS). Oxidation has been carried out ex-situ in a high-pressure cell with subsequent vacuum-transfer and characterization by XPS in ultrahigh vacuum (UHV), as well as using in-situ characterization by synchrotron based near-ambient pressure XPS. On Au(111) alloying of Pd with the substrate competes with oxidation and only sufficiently thick Pd films have been found to oxidize. For Pd on ZnO the oxidation conditions depend on the amount of deposited Pd. Thicker Pd deposits behave similar to bulk Pd, while thinner filmsmore » oxidize already at lower temperatures. Interestingly, for very small amounts of Pd, in-situ XPS shows full oxidation at room temperature and at less than 0.6 mbar O₂ pressure. This indicates a lowering of the kinetic barriers for oxidation of very small supported Pd-clusters. The formed oxide is, however, not stable in UHV and a slow reduction is observed. The instability of this oxide indicates that the Pd-oxide formed at the interface to ZnO may have different chemical properties compared to bulk PdO or surface oxides on Pd.« less

  4. Oxidation of palladium on Au(111) and ZnO(0001) supports

    SciTech Connect

    Lallo, J.; Tenney, S. A.; Kramer, A.; Sutter, P.; Batzill, M.

    2014-10-21

    The oxidation of supported Pd-deposits on Au(111) and ZnO(0001) single crystals has been studied by x- ray photoemission spectroscopy (XPS). Oxidation has been carried out ex-situ in a high-pressure cell with subsequent vacuum-transfer and characterization by XPS in ultrahigh vacuum (UHV), as well as using in-situ characterization by synchrotron based near-ambient pressure XPS. On Au(111) alloying of Pd with the substrate competes with oxidation and only sufficiently thick Pd films have been found to oxidize. For Pd on ZnO the oxidation conditions depend on the amount of deposited Pd. Thicker Pd deposits behave similar to bulk Pd, while thinner films oxidize already at lower temperatures. Interestingly, for very small amounts of Pd, in-situ XPS shows full oxidation at room temperature and at less than 0.6 mbar O₂ pressure. This indicates a lowering of the kinetic barriers for oxidation of very small supported Pd-clusters. The formed oxide is, however, not stable in UHV and a slow reduction is observed. The instability of this oxide indicates that the Pd-oxide formed at the interface to ZnO may have different chemical properties compared to bulk PdO or surface oxides on Pd.

  5. STM study of C60F18 high dipole moment molecules on Au(111)

    NASA Astrophysics Data System (ADS)

    Bairagi, K.; Bellec, A.; Chumakov, R. G.; Menshikov, K. A.; Lagoute, J.; Chacon, C.; Girard, Y.; Rousset, S.; Repain, V.; Lebedev, A. M.; Sukhanov, L. P.; Svechnikov, N. Yu.; Stankevich, V. G.

    2015-11-01

    Scanning tunneling microscopy and spectroscopy studies of C60F18 molecules deposited on Au(111) are reported and compared to C60 molecules both at liquid helium temperature and room temperature (RT). Whereas adsorption and electronic properties of C60F18 single molecules were studied at low temperature (LT), self-assemblies were investigated at RT. In both cases, the fluorine atoms of the C60F18 molecules are pointed towards the surface. Individual C60F18 molecules on Au(111) have a HOMO-LUMO gap of 2.9 eV. The self-assembled islands exhibit a close-packed hexagonal lattice with amorphous borders. The comparison with C60 molecules clearly demonstrates the influence of the C60F18 electric dipole moment (EDM) on the electronic properties of single molecules and on the thermodynamics of self-assembled islands. Besides, the apparent height value of a separate molecule increases in a self-assembly environment as a result of a depolarization phenomenon.

  6. Theoretical study of coupling p-aminothiophenol to hydroazo- and azo-adducts on Au(111).

    PubMed

    Lang, Xiufeng; Liang, Yanhong; Liu, Siyan; Zhao, Shanshan; Lau, Woon-Ming

    2016-09-01

    Aminothiophenol/Au(111) has been adopted as an exemplary model in plasmonics research, including surface-enhanced Raman spectroscopy, due to its high plasmonic-induced spectral-signal enhancement. The present work was aimed at clarifying whether aminothiophenol on Au(111) is chemically stable in the absence of any photo- and plasmonic-induced effects. Briefly, first-principles calculations were employed to track the detailed mechanism of oxidative coupling of p-aminothiophenol (PATP) to its azo-adduct with an N = N bond, i.e., p,p'-dimercaptoazobenzene (DMAB). Our results show the following: first, in the presence of adsorbed O2, PATP fractures its N-H bond and transfers the hydrogen to a nearby oxygen. This pathway is more favorable than the transfer of H to Au, but the activation barrier of 0.9 eV is still too high for the reaction to occur in the absence of thermal-, photo-, or plasmonic-activation. If this bar can be lifted, two such dehydrogenated PATP can couple themselves to form an adduct with a N-N bond, i.e., p,p'-dimercaptohydroazobenzene (DMHAB), and this reaction is exoergic with an energy barrier of 0.57 eV. Again, this step is slow in the absence of moderate thermal activation or photo-/plasmonic-activation. Finally, dehydrogenation of DMHAB gives the azo-adduct of DMAB, and this reaction is spontaneous, with no energy barrier. PMID:27488103

  7. Environment-modulated Kondo phenomena in FePc/Au(111) adsorption systems

    NASA Astrophysics Data System (ADS)

    Wang, Yu; Zheng, Xiao; Yang, Jinlong

    2016-03-01

    Recent scanning tunneling microscopy experiments on electron transport through iron(II) phthalocyanine (FePc) molecules adsorbed on the Au(111) surface have revealed that the measured Kondo conductance signature depends strongly on the specific adsorption site. To understand the physical origin of experimental observations, particularly the variation of Kondo features with the molecular adsorption site, we employ a combined density functional theory (DFT) and hierarchical equations of motion (HEOM) approach to investigate the electronic structure and Kondo correlation in FePc/Au(111) composite systems. The calculation results indicate that, for the on-top adsorption configuration, the two degenerate spin-unpaired dπ orbitals on the Fe center are coupled indirectly through substrate band states, leading to the Fano-like antiresonance line shape in the d I /d V spectra, while for the bridge adsorption configuration, the environment-induced couplings are largely suppressed because of the two different spin-unpaired d orbitals. Therefore, our work suggests that the environment-induced coupling as an essential physical factor could greatly influence the Fano-Kondo features in magnetic molecule/metal composites, and the crucial role of local orbital degeneracy and symmetry is discovered. These findings provide important insights into the electron correlation effects in complex solid-state systems. The usefulness and practicality of the combined DFT+HEOM method is also highlighted.

  8. Ir-induced activation of Au towards CO adsorption: Ir films deposited on Au{111}

    NASA Astrophysics Data System (ADS)

    Zhang, Tianfu; Driver, Stephen M.; Pratt, Stephanie J.; Jenkins, Stephen J.; King, David A.

    2016-06-01

    We have investigated the interaction of CO with Ir/Au{111} bimetallic surfaces, and the influence of morphology changes as Ir moves sub-surface into the Au bulk, using reflection-absorption infrared spectroscopy (RAIRS). The presence of Ir stabilises CO on exposed regions of the Au surface at temperatures up to around 200 K: we attribute this to low-coordinated Au sites, probably associated with lifting of the clean-surface 'herringbone' reconstruction by Ir deposition. The highest density of active Au sites is obtained after annealing the bimetallic surface to 500-600 K: we attribute this to morphology changes associated with the movement of Ir into bulk Au.

  9. NaCl multi-layer islands grown on Au(111)-([Formula: see text]) probed by scanning tunneling microscopy.

    PubMed

    Sun, Xiaonan; Felicissimo, Marcella P; Rudolf, Petra; Silly, Fabien

    2008-12-10

    The growth of multi-layer NaCl islands on Au(111)-([Formula: see text]) surfaces was investigated using scanning tunneling microscopy (STM). We observed that the aspect of the NaCl islands drastically differs depending on the tunneling conditions. It is therefore possible to observe the layers forming an NaCl island or to image the gold reconstruction below the first NaCl layer. Atomically resolved STM images obtained on the first NaCl layer demonstrate that NaCl grows as an epitaxial crystalline film on Au(111)-([Formula: see text]). STM images also suggest that some NaCl layers can be non-crystalline. PMID:21730671

  10. Image potential states at chevron-shaped graphene nanoribbons /Au(111) interfaces

    NASA Astrophysics Data System (ADS)

    Bronner, Christopher; Haase, Anton; Tegeder, Petra

    2015-01-01

    Image potential states (IPSs) have been observed for various adsorbed carbon structures, such as graphene or carbon nanotubes. Graphene nanoribbons (GNRs) are intriguing nanostructures with a significant band gap which promise applications in nanotechnology. In the present paper we employ two-photon photoemission (2PPE) to investigate the unoccupied electronic structure and particularly the IPS of chevron-shaped GNR which are synthesized in a thermally activated on-surface synthesis on Au(111). Angle- and time-resolved 2PPE are utilized to gain further insights into the properties of the IPS. Compared to the pristine surface, reduced effective masses between 0.6 and 0.8 electron masses are observed and the lifetimes of the IPS are below the experimental detection limit, which is in the femtosecond regime. Independent of the concentration of N dopant atoms introduced in the GNR we observe a constant binding energy with respect to the vacuum level of the system.

  11. Role of electronic friction during the scattering of vibrationally excited nitric oxide molecules from Au(111)

    NASA Astrophysics Data System (ADS)

    Monturet, Serge; Saalfrank, Peter

    2010-08-01

    Some time ago, it has been observed that vibrationally highly excited NO(v) molecules (with typical vibrational quantum numbers v≈15 ) lose substantial amounts of vibrational energy when scattering off a Au(111) surface [H. Huang, C. Rettner, D. Auerbach, and A. Wodtke, Science 290, 111 (2000)10.1126/science.290.5489.111]. This has been interpreted as a sign for the breakdown of the Born-Oppenheimer approximation due to vibration-electron coupling. It has been argued that this process cannot be understood on the basis of single-quantum transitions which are typical for “electronic friction” models based on a perturbative treatment of weak vibration-electron couplings. Rather, multiple-quanta transitions characteristic for strong nonadiabatic effects are needed according to recent classical surface hopping calculations involving multiple potential-energy surfaces and model Hamiltonians [N. Shenvi, S. Roy, and J. C. Tully, Science 326, 829 (2009)10.1126/science.1179240]. Here we address the importance and magnitude of electronic friction for NO@Au(111) by using fully quantum-mechanical, parameter-free first-principles theories in reduced dimensions. Periodic density-functional theory calculations are performed to obtain a ground-state potential-energy surface along the desorption and NO-vibration coordinates, and coordinate-resolved, finite NO vibrational lifetimes due to vibration-electron coupling. Using this input, the scattering event is modeled by open-system density-matrix theory in the frame of the coupled-channel-density-matrix method, which allows for the inclusion of energy relaxation of the scattering NO molecules. It is found that within this model at least, electronic friction accounts for the observed vibrational deactivation of NO scattering from gold.

  12. A molecular dynamics study of nanoindentation on a methyl methacrylate ultrathin film on a Au(111) substrate: interface and thickness effects.

    PubMed

    Lee, Wen-Jay; Ju, Shin-Pon; Cheng, Ching-Ho

    2008-12-01

    The molecular dynamics simulation model of nanoindentation is proposed in order to study the mechanical and structural deformation properties of an ultrathin MMA (methyl methacrylate) film on a Au(111) surface. First, the significant differences in the structural arrangement of MMA thin films with different thicknesses are observed. Two layers are apparent in the thinnest MMA thin film next to the Au(111) surface, while three layer structures are apparent in the thicker film. Second, this study examines the indentation tip that penetrates the MMA thin film into the Au(111) substrate in order to understand the influence of the interface on the properties and deformation behavior in both the thin film and substrate. The result shows that the indentation force is influenced both by the layer structure and by the thickness of the MMA film. The thinnest case exhibits different deformation behavior from that of the thicker cases. In addition, the deformation of MMA molecules becomes significant at the interface between the MMA film and the Au(111) surface with the increase of film thickness, and detailed deformation behavior of the Au surface for different thicknesses of MMA film is reported in this paper. Finally, both the rigid and the active models for the indentation tip are utilized in the simulation to examine the interaction differences between the tip and the film and the deformation mechanism. PMID:18986180

  13. The formation of right-handed and left-handed chiral nanopores within a single domain during amino acid self-assembly on Au(111).

    PubMed

    Yang, Sena; Jeon, Aram; Driver, Russell W; Kim, Yeonwoo; Jeon, Eun Hee; Kim, Sehun; Lee, Hee-Seung; Lee, Hangil

    2016-05-25

    We report the formation of both right- and left-handed chiral nanopores within a single domain during the self-assembly of an amino acid derivative on an inert Au(111) surface using STM. DFT calculations employed to rationalize this unusual result identified that intermolecular interactions between chiral, windmill-shaped tetramers are crucial for self-assembly.

  14. Minimum threshold for incipient plasticity in the atomic-scale nanoindentation of Au(111).

    PubMed

    Paul, William; Oliver, David; Miyahara, Yoichi; Grütter, Peter H

    2013-03-29

    The formation of the smallest permanent indentation in a Au(111) surface is studied by scanning tunneling microscopy and atomic force microscopy in ultrahigh vacuum. The 9.5 nm radius W(111) indenter was characterized in situ by field ion microscopy. Elastic and plastic indentations are identified both in the residual impression image and by features in their force-displacement curves such as the sink-in depth, pop-ins, and hysteresis energy. Plasticity is best identified quantitatively in the force-displacement curves by the sink-in depth. The minimum of plastic damage producible in the substrate is associated with an energy budget of ∼70  eV.

  15. Probing the ultrafast electron transfer at the CuPc/Au(111) interface

    SciTech Connect

    Chen Wei; Wang Li; Qi Dongchen; Chen Shi; Gao Xingyu; Wee, Andrew Thye Shen

    2006-05-01

    Core-hole clock spectroscopy and near-edge x-ray-absorption fine structure measurements have been used to investigate the ultrafast electron transfer dynamics at the Copper(II) phthalocyanine (CuPc)/Au(111) interface. It was found that the strong electronic coupling between the first layer of CuPc molecules and Au(111) substrate favors ultrafast electron transfer from the lowest unoccupied molecular orbital of the CuPc molecules to the conduction band of Au(111) in the time scale of {approx}6 fs. In contrast, the intermolecular electron transfer within multilayers of CuPc molecules via the weak van der Waals interaction was much slower.

  16. THERMODYNAMIC PROPERTIES OF THE METALLIC SYSTEM Au(111)-(3×3)R30∘-Pd

    NASA Astrophysics Data System (ADS)

    Chadli, R.; Kheffache, S.; Khater, A.

    2016-02-01

    This work constitutes an analysis of the thermodynamic properties in the ordered metallic surface alloy system Au(111)-(3×3)R30∘-Pd. The equilibrium structural characteristics as well as the thermodynamic functions are examined by the matching method, associated with real space Green’s function formalism, evaluated in the harmonic approximation. Our numerical results, for this metallic system of surface alloy, show in particular a significant dependence between the thermodynamic properties and the coordination number and the values of the force constants.

  17. Characterization of one-dimensional molecular chains of 4,4'-biphenyl diisocyanide on Au(111) by scanning tunneling microscopy

    DOE PAGES

    Zhou, Jing; Li, Yan; Zahl, Percy; Sutter, Peter; Stacchiola, Dario J.; White, Michael G.

    2015-03-14

    The morphology and electronic structure of vapor deposited 4,4'-biphenyldiisocyanide (BPDI) on a Au(111) surface were investigated using variable-temperature scanning tunneling microscopy (STM). When deposited at room temperature, BPDI molecules form one-dimensional molecular chains similar to that recently observed for the structurally related 1,4-phenyl diisocyanide (PDI). Compared to PDI, the longer periodicity for the BPDI molecular chains is consistent with the addition of a second phenyl ring and supports a structural model in which the BPDI molecules lie parallel to the surface and interconnected by Au-adatoms. The molecular chains are mostly aligned along the [110] direction of the Au(111) substrate, butmore » exhibit frequent changes in angle that are consistent with directions between fcc and hcp three-fold hollow sites. Dispersion-corrected density functional theory calculations for one-dimensional chains of BPDI molecules bound end-to-end via their isocyanide groups to Au-adatoms reproduce the observed periodicity of the chains and show that this morphology is energetically favored over upright binding with one free –NC group. The spatially resolved conductance (dI/dV) map for BPDI on Au(111) exhibits a feature centered at -0.67 eV below the Fermi level which are delocalized along the chain with maxima at the Au-adatom and biphenyl positions. This occupied resonant feature is close to that previously observed for the PDI in both photoemission and conductance measurements and is attributed to an occupied interfacial state resulting from BPDI-Au interactions« less

  18. Characterization of one-dimensional molecular chains of 4,4'-biphenyl diisocyanide on Au(111) by scanning tunneling microscopy

    SciTech Connect

    Zhou, Jing; Li, Yan; Zahl, Percy; Sutter, Peter; Stacchiola, Dario J.; White, Michael G.

    2015-03-14

    The morphology and electronic structure of vapor deposited 4,4'-biphenyldiisocyanide (BPDI) on a Au(111) surface were investigated using variable-temperature scanning tunneling microscopy (STM). When deposited at room temperature, BPDI molecules form one-dimensional molecular chains similar to that recently observed for the structurally related 1,4-phenyl diisocyanide (PDI). Compared to PDI, the longer periodicity for the BPDI molecular chains is consistent with the addition of a second phenyl ring and supports a structural model in which the BPDI molecules lie parallel to the surface and interconnected by Au-adatoms. The molecular chains are mostly aligned along the [110] direction of the Au(111) substrate, but exhibit frequent changes in angle that are consistent with directions between fcc and hcp three-fold hollow sites. Dispersion-corrected density functional theory calculations for one-dimensional chains of BPDI molecules bound end-to-end via their isocyanide groups to Au-adatoms reproduce the observed periodicity of the chains and show that this morphology is energetically favored over upright binding with one free –NC group. The spatially resolved conductance (dI/dV) map for BPDI on Au(111) exhibits a feature centered at -0.67 eV below the Fermi level which are delocalized along the chain with maxima at the Au-adatom and biphenyl positions. This occupied resonant feature is close to that previously observed for the PDI in both photoemission and conductance measurements and is attributed to an occupied interfacial state resulting from BPDI-Au interactions

  19. In-Situ Characterization of Electrode-Solution Interfacial Processes by Atomic-Resolution Scanning Tunneling Microscopy and Surface Enhanced Raman Spectroscopy.

    NASA Astrophysics Data System (ADS)

    Gao, Xiaoping

    1992-01-01

    The author's research is directed towards the atomic-molecular-level understanding of electrochemical interfacial processes, utilizing in-situ atomic-resolution scanning tunneling microscopy (STM) and surface enhanced Raman spectroscopy (SERS). The majority of this research effort has focussed on a systematic STM study of potential -induced surface reconstruction of gold single crystal electrodes and combined atomic-resolution STM and surface vibrational spectroscopy as in-situ probes of molecular adsorption and electrooxidation on metal electrodes. We have demonstrated for the first time that truly atomic-resolution STM images of gold surface reconstruction and molecular transformation can be observed at electrochemical interfaces under potential control conditions. The findings illustrate in a more general vein the power of STM for elucidating previously unobtainable details of surface atomic structure at electrochemical interfaces. The STM study shows that Au(111), (100), (110), (311), and (533) are observed to undergo reconstruction at the potentials corresponding to small (ca. 10-15 muc cm^{-2}) negative electrode charges. Some information regarding the mechanisms of the changes in atomic density required for reconstruction can be obtained from time- and potential -dependent sequences of STM images. In-situ potential-dependent STM studies of electrochemical processes of sulfide and iodide on Au(111), carbon monoxide on Rh(111) and (110) in aqueous solutions have been carried out and compared with SER spectra or infrared spectra. The details of potential-dependent adlayer structures and the formation of electrooxidation products, such as S _8 rings, polyiodide chains and crystal films, were observed and the results are in good agreement with the surface vibrational spectra. The orientation of adsorbed benzene and monosubstituted benzenes on gold electrodes have also been studied using SER spectroscopy. The results provide strong evidence that SERS selection

  20. Cluster-size dependent phase transition of Co oxides on Au(111)

    NASA Astrophysics Data System (ADS)

    Li, M.; Altman, E. I.

    2014-01-01

    The surface structure of Co oxide nanoparticles supported on Au(111) was studied using scanning tunneling microscopy (STM) and ultra-violet photoelectron spectroscopy (UPS). Initial Co oxide growth at oxygen pressures orders of magnitude above those required to form bulk Co3O4 resulted solely in small 2-D CoO islands, exhibiting a moiré surface characteristic of the rocksalt (111) surface; continued growth led to a transition to fully oxidized 3-D Co3O4 spinel clusters. The CoO-Co3O4 transition is reversible by reduction in vacuum. It is shown that the stabilization of the reduced phase at low coverages can be explained by the higher surface energy of the support and the Co3O4 spinel structure; since a bilayer is the smallest repeat unit of this structure, oxidation increases the exposed area of the high surface energy substrate. In addition, the 2D to 3D transition required to form Co3O4 increases the occupancy of high energy edge sites, thus further stabilizing small CoO clusters against oxidation. The results show how support interactions and particle size can be used to tune the stability of oxide phases.

  1. UHV deposition and characterization of a mononuclear iron(III) β-diketonate complex on Au(111)

    PubMed Central

    Cimatti, Irene; Ninova, Silviya; Lanzilotto, Valeria; Malavolti, Luigi; Rigamonti, Luca; Cortigiani, Brunetto; Mannini, Matteo; Magnano, Elena; Bondino, Federica; Totti, Federico; Cornia, Andrea

    2014-01-01

    Summary The adsorption of the sterically hindered β-diketonate complex Fe(dpm)3, where Hdpm = dipivaloylmethane, on Au(111) was investigated by ultraviolet photoelectron spectroscopy (UPS) and scanning tunnelling microscopy (STM). The high volatility of the molecule limited the growth of the film to a few monolayers. While UPS evidenced the presence of the β-diketonate ligands on the surface, the integrity of the molecule on the surface could not be assessed. The low temperature STM images were more informative and at submonolayer coverage they showed the presence of regular domains characterized by a flat morphology and height of ≈0.3 nm. Along with these domains, tetra-lobed features adsorbed on the kinks of the herringbone were also observed. DFT-simulated images of the pristine molecule and its possible decomposition products allowed to assess the partial fragmentation of Fe(dpm)3 upon adsorption on the Au(111) surface. Structural features with intact molecules were only observed for the saturation coverage. An ex situ prepared thick film of the complex was also investigated by X-ray magnetic circular dichroism (XMCD) and features typical of high-spin iron(III) in octahedral environment were observed. PMID:25551042

  2. Tuning electronic properties of novel metal oxide nanocrystals using interface interactions: MoO3 monolayers on Au(111)

    SciTech Connect

    Quek, S; Biener, M M; Biener, J; Friend, C M; Kaxiras, E

    2004-04-20

    Metal oxide nanocrystals deposited on metal surfaces have novel electronic properties due to interface and nanoscale effects. Crystals and nanoscale ribbons of MoO{sub 3} are highly effective catalysts and field emitters. This renders MoO{sub 3} an interesting prototype. Whilst MoO{sub 3} exists as bilayers in the bulk crystal5, in this work, monolayer MoO{sub 3} nanocrystals were grown epitaxially on Au(111). Ab initio calculations reveal that Au stabilizes the MoO{sub 3} monolayer through electronic charge redistribution at the interface. The Mo-O bonds are able to rotate about one another, allowing the MoO{sub 3} monolayer to adjust to the Au lattice. As a result, the monolayer is semimetallic, unlike bulk MoO{sub 3} which is semiconducting. This remarkable flexibility of the oxide lattice suggests the possibility of tuning electronic properties of transition metal oxides via interface interactions. The overall surface pattern obtained is affected by an interplay between the Au(111) surface reconstruction and the edges of the deposited MoO{sub 3} islands.

  3. Vibrational energy transfer near a dissociative adsorption transition state: State-to-state study of HCl collisions at Au(111).

    PubMed

    Geweke, Jan; Shirhatti, Pranav R; Rahinov, Igor; Bartels, Christof; Wodtke, Alec M

    2016-08-01

    In this work we seek to examine the nature of collisional energy transfer between HCl and Au(111) for nonreactive scattering events that sample geometries near the transition state for dissociative adsorption by varying both the vibrational and translational energy of the incident HCl molecules in the range near the dissociation barrier. Specifically, we report absolute vibrational excitation probabilities for HCl(v = 0 → 1) and HCl(v = 1 → 2) scattering from clean Au(111) as a function of surface temperature and incidence translational energy. The HCl(v = 2 → 3) channel could not be observed-presumably due to the onset of dissociation. The excitation probabilities can be decomposed into adiabatic and nonadiabatic contributions. We find that both contributions strongly increase with incidence vibrational state by a factor of 24 and 9, respectively. This suggests that V-T as well as V-EHP coupling can be enhanced near the transition state for dissociative adsorption at a metal surface. We also show that previously reported HCl(v = 0 → 1) excitation probabilities [Q. Ran et al., Phys. Rev. Lett. 98, 237601 (2007)]-50 times smaller than those reported here-were influenced by erroneous assignment of spectroscopic lines used in the data analysis. PMID:27497574

  4. Vibrational energy transfer near a dissociative adsorption transition state: State-to-state study of HCl collisions at Au(111)

    NASA Astrophysics Data System (ADS)

    Geweke, Jan; Shirhatti, Pranav R.; Rahinov, Igor; Bartels, Christof; Wodtke, Alec M.

    2016-08-01

    In this work we seek to examine the nature of collisional energy transfer between HCl and Au(111) for nonreactive scattering events that sample geometries near the transition state for dissociative adsorption by varying both the vibrational and translational energy of the incident HCl molecules in the range near the dissociation barrier. Specifically, we report absolute vibrational excitation probabilities for HCl(v = 0 → 1) and HCl(v = 1 → 2) scattering from clean Au(111) as a function of surface temperature and incidence translational energy. The HCl(v = 2 → 3) channel could not be observed—presumably due to the onset of dissociation. The excitation probabilities can be decomposed into adiabatic and nonadiabatic contributions. We find that both contributions strongly increase with incidence vibrational state by a factor of 24 and 9, respectively. This suggests that V-T as well as V-EHP coupling can be enhanced near the transition state for dissociative adsorption at a metal surface. We also show that previously reported HCl(v = 0 → 1) excitation probabilities [Q. Ran et al., Phys. Rev. Lett. 98, 237601 (2007)]—50 times smaller than those reported here—were influenced by erroneous assignment of spectroscopic lines used in the data analysis.

  5. Mechanistic understanding of hydrogenation of acetaldehyde on Au(111): A DFT investigation

    NASA Astrophysics Data System (ADS)

    Meng, Qingsen; Shen, Yongli; Xu, Jing; Ma, Xinbin; Gong, Jinlong

    2012-11-01

    This paper describes the reaction pathways for hydrogenation of acetaldehyde on atomic hydrogen pre-adsorbed Au(111) employing density functional theory (DFT) calculations. All the surface species involved in the reaction scheme have low diffusion barriers, suggesting that the rearrangement and movement of these species on the surface are facile under reaction condition. The hydroxyethyl is proposed to be the intermediate for the hydrogenation of acetaldehyde, and the activation energy for its formation is 0.37 eV. Additionally, the coupling reaction of hydroxyethyl and acetaldehyde - resulting in the formation of the ethylidene ethylene glycol (CH3C*HOCH(CH3)OH) species - also readily occurs at the reaction condition. Two-dimensional (2-D) polyacetaldehyde ((CH3CHO)2) can be easily hydrogenated to ethylidene ethylene glycol or ethoxy hemiacetal (CH3CH2OCH(CH3)O*); the latter can be converted to ethanol and acetaldehyde via further hydrogenation. As the hydrogenation products of ethylidene ethylene glycol and ethoxy hemiacetal, ethoxyethanol (CH3CH2OCH(CH3)OH) can be deeply hydrogenated to hydroxyethyl and ethanol. Our calculations also suggest that the formation of an ethoxyl intermediate is not likely, which agrees with the experimental observation that no deuterated acetaldehydes have been detected in isotopic measurements.

  6. Structural Changes in Self-Catalyzed Adsorption of Carbon Monoxide on 1,4-Phenylene Diisocyanide Modified Au(111)

    SciTech Connect

    Kestell, John; Boscoboinik, J. Anibal; Cheng, Lanxia; Garvey, Michael; Bennett, Dennis W.; Tysoe, Wilfred T.

    2015-07-23

    The self-accelerated adsorption of CO on 1,4-phenylene diisocyanide (PDI)-derived oligomers on Au(111) is explored by reflection–absorption infrared spectroscopy and scanning tunneling microscopy. PDI incorporates gold adatoms from the Au(111) surface to form one-dimensional —(Au–PDI)n— chains that can also connect between gold nanoparticles on mica to form a conductive pathway between them. CO adsorption occurs in two stages; it first adsorbs adjacent to the oligomers that move to optimize CO adsorption. Further CO exposure induces PDI decoordination to form Au–PDI adatom complexes thereby causing the conductivity of a PDI-linked gold nanoparticle array on mica to decrease to act as a chemically drive molecular switch. This simple system enables the adsorption process to be explored in detail. DFT calculations reveal that both the —(Au–PDI)n— oligomer chain and the Au–PDI adatom complex are stabilized by coadsorbed CO. A kinetic “foot-in-the-door” model is proposed in which fluctuations in PDI coordination allow CO to diffuse into the gap between gold adatoms to prevent the PDI from reattaching, thereby allowing additional CO to adsorb, to provide kinetic model for allosteric CO adsorption on PDI-covered gold.

  7. Structural Changes in Self-Catalyzed Adsorption of Carbon Monoxide on 1,4-Phenylene Diisocyanide Modified Au(111)

    DOE PAGES

    Kestell, John; Boscoboinik, J. Anibal; Cheng, Lanxia; Garvey, Michael; Bennett, Dennis W.; Tysoe, Wilfred T.

    2015-07-23

    The self-accelerated adsorption of CO on 1,4-phenylene diisocyanide (PDI)-derived oligomers on Au(111) is explored by reflection–absorption infrared spectroscopy and scanning tunneling microscopy. PDI incorporates gold adatoms from the Au(111) surface to form one-dimensional —(Au–PDI)n— chains that can also connect between gold nanoparticles on mica to form a conductive pathway between them. CO adsorption occurs in two stages; it first adsorbs adjacent to the oligomers that move to optimize CO adsorption. Further CO exposure induces PDI decoordination to form Au–PDI adatom complexes thereby causing the conductivity of a PDI-linked gold nanoparticle array on mica to decrease to act as a chemicallymore » drive molecular switch. This simple system enables the adsorption process to be explored in detail. DFT calculations reveal that both the —(Au–PDI)n— oligomer chain and the Au–PDI adatom complex are stabilized by coadsorbed CO. A kinetic “foot-in-the-door” model is proposed in which fluctuations in PDI coordination allow CO to diffuse into the gap between gold adatoms to prevent the PDI from reattaching, thereby allowing additional CO to adsorb, to provide kinetic model for allosteric CO adsorption on PDI-covered gold.« less

  8. Enhanced fullerene–Au(111) coupling in (2√3 × 2√3)R30° superstructures with intermolecular interactions

    PubMed Central

    Paßens, Michael; Waser, Rainer

    2015-01-01

    Summary Disordered and uniform (2√3 × 2√3)R30° superstructures of fullerenes on the Au(111) surface have been studied using scanning tunneling microscopy and spectroscopy. It is shown that the deposition and growth process of a fullerene monolayer on the Au(111) surface determine the resulting superstructure. The supply of thermal energy is of importance for the activation of a Au vacancy forming process and thus, one criterion for the selection of the respective superstructure. However, here it is depicted that a vacancy–adatom pair can be formed even at room temperature. This latter process results in C60 molecules that appear slightly more bright in scanning tunnelling microscopy images and are identified in disordered (2√3 x 2√3)R30° superstructures based on a detailed structure analysis. In addition, these slightly more bright C60 molecules form uniform (2√3 x 2√3)R30° superstructures, which exhibit intermolecular interactions, likely mediated by Au adatoms. Thus, vacancy–adatom pairs forming at room temperature directly affect the resulting C60 superstructure. Differential conductivity spectra reveal a lifting of the degeneracy of the LUMO and LUMO+1 orbitals in the uniform (2√3 x 2√3)R30° superstructure and in addition, hybrid fullerene–Au(111) surface states suggest partly covalent interactions. PMID:26199846

  9. Controlling the stereochemistry and regularity of butanethiol self-assembled monolayers on au(111).

    PubMed

    Yan, Jiawei; Ouyang, Runhai; Jensen, Palle S; Ascic, Erhad; Tanner, David; Mao, Bingwei; Zhang, Jingdong; Tang, Chunguang; Hush, Noel S; Ulstrup, Jens; Reimers, Jeffrey R

    2014-12-10

    The rich stereochemistry of the self-assembled monolayers (SAMs) of four butanethiols on Au(111) is described, the SAMs containing up to 12 individual C, S, or Au chiral centers per surface unit cell. This is facilitated by synthesis of enantiomerically pure 2-butanethiol (the smallest unsubstituted chiral alkanethiol), followed by in situ scanning tunneling microscopy (STM) imaging combined with density functional theory molecular dynamics STM image simulations. Even though butanethiol SAMs manifest strong headgroup interactions, steric interactions are shown to dominate SAM structure and chirality. Indeed, steric interactions are shown to dictate the nature of the headgroup itself, whether it takes on the adatom-bound motif RS(•)Au(0)S(•)R or involves direct binding of RS(•) to face-centered-cubic or hexagonal-close-packed sites. Binding as RS(•) produces large, organizationally chiral domains even when R is achiral, while adatom binding leads to rectangular plane groups that suppress long-range expression of chirality. Binding as RS(•) also inhibits the pitting intrinsically associated with adatom binding, desirably producing more regularly structured SAMs.

  10. Functional nicotinic acetylcholine receptor reconstitution in Au(111)-supported thiolipid monolayers.

    PubMed

    Pissinis, Diego E; Diaz, Carolina; Maza, Eliana; Bonini, Ida C; Barrantes, Francisco J; Salvarezza, Roberto C; Schilardi, Patricia L

    2015-10-14

    The insertion and function of the muscle-type nicotinic acetylcholine receptor (nAChR) in Au(111)-supported thiolipid self-assembled monolayers have been studied by atomic force microscopy (AFM), surface plasmon resonance (SPR), and electrochemical techniques. It was possible for the first time to resolve the supramolecular arrangement of the protein spontaneously inserted in a thiolipid monolayer in an aqueous solution. Geometric supramolecular arrays of nAChRs were observed, most commonly in a triangular form compatible with three nAChR dimers of ∼20 nm each. Addition of the full agonist carbamoylcholine activated and opened the nAChR ion channel, as revealed by the increase in capacitance relative to that of the nAChR-thiolipid system under basal conditions. Thus, the self-assembled system appears to be a viable biomimetic model to measure ionic conductance mediated by ion-gated ion channels under different experimental conditions, with potential applications in biotechnology and pharmacology. PMID:26355753

  11. Adsorption and oligomerization of 1,3-phenylene diisocyanide on Au(111)

    DOE PAGES

    Kestell, John; Walker, Joshua; Bai, Yun; Boscoboinik, J. Anibal; Garvey, Michael; Tysoe, Wilfred T.

    2016-04-18

    The adsorption and self-assembly of 1,3-phenylene diisocyanide (1,3-PDI) are studied on Au(111) using reflection–adsorption infrared spectroscopy (RAIRS), scanning tunneling microscopy (STM), and temperature-programmed desorption (TPD) supplemented by density functional theory (DFT) calculations and the results compared with the structures formed from 1,4-PDI where it assembled to form –(Au–PDI)– oligomer chains that incorporate gold adatoms. The infrared spectra display a single isocyanide feature consistent with the isocyanide binding to gold adatoms, while DFT calculations confirm that isocyanide binding to gold adatoms is more energetically favorable than binding to the surface. STM images show that 1,3-PDI forms zigzag chains containing hairpin bendsmore » that cause the chains to double back on each other, consistent with the 120° angle between the isocyanide groups. Hexagonal structural motifs are also observed that are proposed to be due to the self-assembly of three isocyanides as well as small structures that are assigned to 1,3-PDI dimers. Furthermore, the results suggest that the formation of gold-containing oligomers from isocyanide-containing molecules is a general phenomenon.« less

  12. Functional nicotinic acetylcholine receptor reconstitution in Au(111)-supported thiolipid monolayers

    NASA Astrophysics Data System (ADS)

    Pissinis, Diego E.; Diaz, Carolina; Maza, Eliana; Bonini, Ida C.; Barrantes, Francisco J.; Salvarezza, Roberto C.; Schilardi, Patricia L.

    2015-09-01

    The insertion and function of the muscle-type nicotinic acetylcholine receptor (nAChR) in Au(111)-supported thiolipid self-assembled monolayers have been studied by atomic force microscopy (AFM), surface plasmon resonance (SPR), and electrochemical techniques. It was possible for the first time to resolve the supramolecular arrangement of the protein spontaneously inserted in a thiolipid monolayer in an aqueous solution. Geometric supramolecular arrays of nAChRs were observed, most commonly in a triangular form compatible with three nAChR dimers of ~20 nm each. Addition of the full agonist carbamoylcholine activated and opened the nAChR ion channel, as revealed by the increase in capacitance relative to that of the nAChR-thiolipid system under basal conditions. Thus, the self-assembled system appears to be a viable biomimetic model to measure ionic conductance mediated by ion-gated ion channels under different experimental conditions, with potential applications in biotechnology and pharmacology.

  13. The Role of Tris(2-carboxyethyl)phosphine Reducing Agent in the Controlled Formation of α,ω-Alkanedithiols Monolayers on Au(111) with Monocoordinated and Bicoordinated Configurations.

    PubMed

    Euti, Esteban M; Vélez-Romero, Patricio; Leiva, Ezequiel P M; Macagno, Vicente A; Paredes-Olivera, Patricia A; Patrito, E Martín; Cometto, Fernando P

    2016-09-20

    The addition of the reducing agent tris(2-carboxyethyl) phosphine (TCEP) during the formation of α,ω-alkanedithiols monolayers on Au(111) using the immersion method produces the assembly of monolayers with bicoordinated molecules (both S-terminal groups bound to the surface) that have a reductive desorption potential that is more positive than for monolayers with monocoordinated molecules in a standing up configuration. We show that the use of TCEP either during formation of the monolayer or as a post treatment procedure allows the controlled formation of monolayers with bicoordinated or monocoordinated configurations. Density functional theory (DFT) calculations were performed to elucidate the role of TCEP in the formation of the bicoordinated configuration. We investigated the TCEP-dithiol interaction in ethanol solvent as well as the coadsorption of trimethylphosphine with 1,2-ethanedithiol on Au(111). The Brønsted base character of the phosphine facilitates the H exchange from the -SH groups of the dithiol to the phosphorus atom of TCEP with very low activation energy barriers, thus allowing the thiolate groups to bind to the Au(111) surface, thus yielding the bicoordinated configuration. Dithiol lifting mechanisms such as H exchange between S atoms and the formation of intra/inter layer disulfide bonds have much higher energy barriers. PMID:27579725

  14. Molecular alligator clips: a theoretical study of adsorption of S, Se and S H on Au(111)

    NASA Astrophysics Data System (ADS)

    Mankefors, S.; Grigoriev, A.; Wendin, G.

    2003-08-01

    For the binding of thiols to Au, the Au-S interaction is decisive for the geometry, bonding strength and transmissivity of the metal-molecule interface. Using ab initio methods we investigate the adsorption of sulfur (S) on the Au(111) surface for different coverages between 0.25 and 1.0 monolayers (ML). Corresponding geometries with adsorbed Se are included to establish possible differences between S- and Se-based metal-molecule interfaces. We furthermore investigate hydrogenation of sulfur-covered Au(111) surfaces to establish the energetics and resulting geometry of adsorption of S-H groups on clean Au(111), using it as a simple model system. For the relatively low coverage of 0.25 ML the S and Se atoms are found to prefer the in-hollow sites, with Se displaying a substantially stronger bond. Increasing the coverage leads to depletion of available free charge in the gold surface, which weakens the bonds to the S (Se). Due to the more extensive hybridization, Se is more insensitive to the exact geometry, and the stacking fault position only costs 0.04 eV. At even higher coverage (0.75 ML) the adsorbed atoms hybridize internally and form triatomic molecules situated on top of the Au surface atoms. In S (Se) rich environments this turns out to be the most stable configuration investigated, while in S (Se) poor conditions the surface will adsorb all available S (Se). Forcing the system to adsorb atoms beyond this coverage increases the total energy. For all physically realizable coverages the Au-Se bond is found to be geq0.25 eV stronger than the corresponding Au-S bond. The Se bond also displays a higher degree of metallicity and should be expected to make a better head group for thiols, for example; this is relevant for both bonding and conductivity. Turning to the hydrogenated S systems we find that surfaces with a high coverage of S only weakly bind H at low partial hydrogenation, while H adsorption in systems with medium and low S concentrations is found to be

  15. Adsorption phenomena of cubane-type tetranuclear Ni(II) complexes with neutral, thioether-functionalized ligands on Au(111)

    NASA Astrophysics Data System (ADS)

    Heß, Volkmar; Matthes, Frank; Bürgler, Daniel E.; Monakhov, Kirill Yu.; Besson, Claire; Kögerler, Paul; Ghisolfi, Alessio; Braunstein, Pierre; Schneider, Claus M.

    2015-11-01

    The controlled and intact deposition of molecules with specific properties onto surfaces is an emergent field impacting a wide range of applications including catalysis, molecular electronics, and quantum information processing. One strategy is to introduce grafting groups functionalized to anchor to a specific surface. While thiols and disulfides have proven to be quite effective in combination with gold surfaces, other S-containing groups have received much less attention. Here, we investigate the surface anchoring and organizing capabilities of novel charge-neutral heterocyclic thioether groups as ligands of polynuclear nickel(II) complexes. We report on the deposition of a cubane-type {Ni4} (= [Ni(μ3-Cl)Cl(HL·S)]4) single-molecule magnet from dichloromethane solution on a Au(111) surface, investigated by scanning tunneling microscopy, X-ray photoelectron spectroscopy, and low-energy electron diffraction, both immediately after deposition and after subsequent post-annealing. The results provide strong evidence for partial decomposition of the coordination complex upon deposition on the Au(111) surface that, however, leaves the magnetic {Ni4Cl4n} (n = 1 or 2) core intact. Only post-annealing above 480 K induces further decomposition and fragmentation of the {Ni4Cl4n} core. The detailed insight into the chemisorption-induced decomposition pathway not only provides guidelines for the deposition of thioether-functionalized Ni(II) complexes on metallic surfaces but also reveals opportunities to use multidentate organic ligands decorated with thioether groups as transporters for highly unstable inorganic structures onto conducting surfaces, where they are stabilized retaining appealing electronic and magnetic properties.

  16. Construction of single-crystalline supramolecular networks of perchlorinated hexa-peri-hexabenzocoronene on Au(111)

    SciTech Connect

    Zhang, Yi; Zhang, Yanfang; Li, Geng; Lu, Jianchen; Du, Shixuan E-mail: hjgao@iphy.ac.cn; Gao, Hong-Jun E-mail: hjgao@iphy.ac.cn; Lin, Xiao; Tan, Yuanzhi; Feng, Xinliang; Müllen, Klaus

    2015-03-14

    The self-assembly of the perchlorinated hexa-peri-hexabenzocoronene (PCHBC) molecules on Au(111) has been studied by a low temperature scanning tunneling microscopy (STM) combining with density functional theory based first principle calculations. Highly ordered supramolecular networks with single domains limited by the terraces are formed on Au(111) substrate. High resolution images of the PCHBC molecules, confirmed by first principle simulations, are obtained. It reveals the close-packed arrangement of the PCHBC molecules on Au(111). The calculated charge distribution of PCHBC molecules shows the existence of attractive halogen–halogen interaction between neighboring molecules. Compared with the disordered adsorption of hexa-peri-hexabenzocoronene on Au(111), we conclude that the formation of attractive ClCl interactions between neighbors is the key factor to form the highly ordered, close-packed networks. Due to the steric hindrance resulted from the peripheral chlorine atoms, the PCHBC molecule is contorted and forms the doubly concave conformation, which is different from the hexa-peri-hexabenzocoronene with a planar structure. By using this supramolecular network as a template, we deposited C{sub 60} molecules on it at room temperature with low coverage. The STM images taken at low temperature show that the C{sub 60} molecules are mono-dispersed on the networks and adsorb on top of the PCHBC molecules, forming a typical concave-convex host-guest system.

  17. Energy level alignment of self-assembled linear chains of benzenediamine on Au(111) from first principles

    NASA Astrophysics Data System (ADS)

    Li, Guo; Rangel, Tonatiuh; Liu, Zhen-Fei; Cooper, Valentino R.; Neaton, Jeffrey B.

    2016-03-01

    Using density functional theory (DFT) with a van der Waals density functional, we calculate the adsorption energetics and geometry of benzenediamine (BDA) molecules on Au(111) surfaces. Our results demonstrate that the reported self-assembled linear chain structure of BDA, stabilized via hydrogen bonds between amine groups, is energetically favored over previously studied monomeric phases. Moreover, using a model, which includes nonlocal polarization effects from the substrate and the neighboring molecules and incorporates many-body perturbation theory calculations within the GW approximation, we obtain approximate self-energy corrections to the DFT highest occupied molecular orbital (HOMO) energy associated with BDA adsorbate phases. We find that, independent of coverage, the HOMO energy of the linear chain phase is lower relative to the Fermi energy than that of the monomer phase, and in good agreement with values measured with ultraviolet photoelectron spectroscopy and x-ray photoelectron spectroscopy.

  18. Communication: Energy transfer and reaction dynamics for DCl scattering on Au(111): An ab initio molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Kolb, Brian; Guo, Hua

    2016-07-01

    Scattering and dissociative chemisorption of DCl on Au(111) are investigated using ab initio molecular dynamics with a slab model, in which the top two layers of Au are mobile. Substantial kinetic energy loss in the scattered DCl is found, but the amount of energy transfer is notably smaller than that observed in the experiment. On the other hand, the dissociative chemisorption probability reproduces the experimental trend with respect to the initial kinetic energy, but is about one order of magnitude larger than the reported initial sticking probability. While the theory-experiment agreement is significantly improved from the previous rigid surface model, the remaining discrepancies are still substantial, calling for further scrutiny in both theory and experiment.

  19. Adlayer structure of octa-alkoxy-substituted copper(II) phthalocyanine on Au(111) by electrochemical scanning tunneling microscopy.

    PubMed

    Wang, Li; Ou-Yang, Liangyue; Yau, Shueh-Lin

    2008-01-01

    Electrochemical scanning tunneling microscopy (ECSTM) has been used to examine the adlayer of octa-alkoxy-substituted copper(II) phthalocyanines (CuPc(OC(8)H(17))(8)) on Au(111) in 0.1 M HClO(4), where the molecular adlayer was prepared by spontaneous adsorption from a benzene solution containing this molecule. Topography STM scans revealed long-range ordered, interweaved arrays of CuPc(OC(8)H(17))(8) with coexistent rectangular and hexagonal symmetries. High-quality STM molecular resolution yielded the internal molecular structure and the orientation of CuPc(OC(8)H(17))(8) admolecules. These STM results could shed insight into the method of generating ordered molecular assemblies of phthalocyanine molecules with long-chained substitutes on metal surface.

  20. Energy level alignment of self-assembled linear chains of benzenediamine on Au(111) from first principles

    DOE PAGES

    Li, Guo; Rangel, Tonatiuh; Liu, Zhen -Fei; Cooper, Valentino R.; Neaton, Jeffrey B.

    2016-03-24

    Using density functional theory (DFT) with van der Waals functionals, we calculate the adsorption energetics and geometry of benzenediamine (BDA) molecules on Au(111) surfaces. Our results demonstrate that the reported self-assembled linear chain structure of BDA, stabilized via hydrogen bonds between amine groups, is energetically favored over previously-studied monomeric phases. Moreover, using a model based on many-body perturbation theory within the GW approximation, we obtain approximate self-energy corrections to the DFT highest occupied molecular orbital (HOMO) energy associated with BDA adsorbate phases. As a result, we find that, independent of coverage, the HOMO energy of the linear chain phase ismore » lower relative to the Fermi energy than that of the monomer phase, and in good agreement with values measured with ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy.« less

  1. Surface characterization of platinum electrodes.

    PubMed

    Solla-Gullón, José; Rodríguez, Paramaconi; Herrero, Enrique; Aldaz, Antonio; Feliu, Juan M

    2008-03-14

    The quantitative analysis of the different surface sites on platinum samples is attempted from pure voltammetric data. This analysis requires independent knowledge of the fraction of two-dimensional (111) and (100) domains. Specific site-probe reactions are employed to achieve this goal. Irreversibly-adsorbed bismuth and tellurium have been revealed to be sensitive to the presence of (111) terrace domains of different width whereas almost all sites involved in (100) ordered domains have been characterized through germanium adatoms. The experimental protocol follows that used with well-defined single-crystal electrodes and, therefore, requires careful control of the surface cleanliness. Platinum basal planes and their vicinal stepped surfaces have been employed to obtain calibration plots between the charge density measured under the adatom redox peak, specific for the type of surface site, and the corresponding terrace size. The evaluation of the (100) bidimensional domains can also be achieved using the voltammetric profiles, once the fraction of (111) ordered domains present in the polyoriented platinum has been determined and their featureless contribution has been subtracted from the whole voltammetric response. Using that curve, it is possible to perform a deconvolution of the adsorption states of the polycrystalline sample different from those related to (111) domains. The fraction of (100)-related states in the deconvoluted voltammogram can then be compared to that expected from the independent estimation coming from the charge involved in the redox process undergone by the irreversibly-adsorbed germanium and thus check the result of the deconvolution. The information about the surface-site distribution can also be applied to analyze the voltammetric profile of nanocrystalline platinum electrodes. PMID:18309392

  2. The Effect of Ring Substitution Position on the Structural Conformation of Mercaptobenzoic Acid Self-Assembled Monolayers on Au(111)

    SciTech Connect

    Lee, J; Willey, T; Nilsson, J; Terminello, L; De Yoreo, J; van Buuren, T

    2006-04-12

    Near edge X-ray absorption fine structure (NEX-AFS) spectroscopy, photoemission spectroscopy (PES) and contact angle measurements have been used to examine the structure and bonding of self-assembled monolayers (SAMs) prepared on Au(111) from the positional isomers of mercaptobenzoic acid (MBA). The isomer of MBA and solvent chosen in SAM preparation has considerable bearing upon film morphology. Carbon K-edge NEXAFS measurements indicate that the monomers of 2-, 3- and 4-MBA have well-defined orientations within their respective SAMs. Monomers of 3- and 4-MBA assume an upright orientation on the Au substrates in monolayers prepared using an acetic acid in ethanol solvent. The aryl ring and carboxyl group of these molecules are tilted from the surface normal by a colatitudal angle of {approx} 30{sup o}. Preparation of 4-MBA SAMs using pure ethanol solvent, a more traditional means of synthesis, had no appreciable effect upon the monomer orientation. Nonetheless, S(2p) PES measurements illustrate that it results in extensive bilayer formation via carboxyl group hydrogen-bonding between 4-MBA monomers. In 2-MBA monolayers prepared using acetic acid/ethanol solvent, the monomers adopt a more prostrate orientation on the Au substrates, in which the aryl ring and carboxyl group of the molecules are tilted {approx} 50{sup o} from the surface normal. This configuration is consistent with an interaction between both the mercaptan sulfur and carboxyl group of 2-MBA with the underlying substrate. S(2p) and C(1s) PES experiments provide supporting evidence for a bidentate interaction between 2-MBA and Au(111).

  3. Underpotential deposition of Cu on Au(111) in sulfate-containing electrolytes: A theoretical and experimental study

    NASA Astrophysics Data System (ADS)

    Zhang, Jun; Sung, Yung-Eun; Rikvold, Per Arne; Wieckowski, Andrzej

    1996-04-01

    We study the underpotential deposition of Cu on single-crystal Au(111) electrodes in sulfate-containing electrolytes by a combination of computational statistical-mechanics based lattice-gas modeling and experiments. The experimental methods are in situ cyclic voltammetry and coulometry and ex situ Auger electron spectroscopy and low-energy electron diffraction. The experimentally obtained voltammetric current and charge densities and adsorbate coverages are compared with the predictions of a two-component lattice-gas model for the coadsorption of Cu and sulfate. This model includes effective, lateral interactions out to fourth-nearest neighbors. Using group-theoretical ground-state calculations and Monte Carlo simulations, we estimate effective electrovalences and lateral adsorbate-adsorbate interactions so as to obtain overall agreement with experiments, including both our own and those of other groups. In agreement with earlier work, we find a mixed (√3×√3) phase consisting of 2/3 monolayer Cu and 1/3 monolayer sulfate at intermediate electrode potentials, delimited by phase transitions at both higher and lower potentials. Our approach provides estimates of the effective electrovalences and lateral interaction energies, which cannot yet be calculated by first-principles methods.

  4. Rotational homogeneity in graphene grown on Au(111)

    NASA Astrophysics Data System (ADS)

    Wofford, Joseph; Starodub, Elena; Walter, Andrew; Nie, Shu; Bostwick, Aaron; Bartelt, Norman; Thürmer, Konrad; Rotenberg, Eli; McCarty, Kevin; Dubon, Oscar

    2012-02-01

    The set of properties offered by the (111) surface of gold makes it intriguing as a platform on which to study the fundamental processes that underpin graphene growth on metals. Among these are the low carbon solubility and an interaction strength with graphene that is predicted to be smaller than most transition metals. We have investigated this synthesis process using low-energy electron microscopy and diffraction to monitor the sample surface in real time, and found that the resulting graphene film possesses a remarkable degree of rotational homogeneity. The dominant orientation of the graphene is aligned with the Au lattice, with a small minority rotated by 30 degrees. The origins of this in-plane structuring are puzzling because angularly resolved photo-emission spectroscopy and scanning tunneling microscopy experiments both suggest only a relatively small interaction between the two materials. Finally, the implications of these findings for the growth of high structural-quality graphene films are discussed.

  5. Nanometer scale mechanical properties of Au(111) thin films

    SciTech Connect

    Salmeron, M.; Folch, A.; Neubauer, G.

    1992-11-01

    The mechanical properties of gold films of (111) orientation were studied as a function of load when contacted by a single asperity Pt-Rh alloy tip. The interaction forces were measured in the direction perpendicular to the surface. The contribution of various types of forces (van der Waals, capillarity from contaminants, and metallic adhesion) in the process of contact was determined. We investigated the elastic and plastic response of the gold film as a function of applied load by examination of the contact area in subsequent imaging with STM and AFM.

  6. Ab initio molecular dynamics calculations on scattering of hyperthermal H atoms from Cu(111) and Au(111).

    PubMed

    Kroes, Geert-Jan; Pavanello, Michele; Blanco-Rey, María; Alducin, Maite; Auerbach, Daniel J

    2014-08-01

    Energy loss from the translational motion of an atom or molecule impinging on a metal surface to the surface may determine whether the incident particle can trap on the surface, and whether it has enough energy left to react with another molecule present at the surface. Although this is relevant to heterogeneous catalysis, the relative extent to which energy loss of hot atoms takes place to phonons or electron-hole pair (ehp) excitation, and its dependence on the system's parameters, remain largely unknown. We address these questions for two systems that present an extreme case of the mass ratio of the incident atom to the surface atom, i.e., H + Cu(111) and H + Au(111), by presenting adiabatic ab initio molecular dynamics (AIMD) predictions of the energy loss and angular distributions for an incidence energy of 5 eV. The results are compared to the results of AIMDEFp calculations modeling energy loss to ehp excitation using an electronic friction ("EF") model applied to the AIMD trajectories, so that the energy loss to the electrons is calculated "post" ("p") the computation of the AIMD trajectory. The AIMD calculations predict average energy losses of 0.38 eV for Cu(111) and 0.13-0.14 eV for Au(111) for H-atoms that scatter from these surfaces without penetrating the surface. These energies closely correspond with energy losses predicted with Baule models, which is suggestive of structure scattering. The predicted adiabatic integral energy loss spectra (integrated over all final scattering angles) all display a lowest energy peak at an energy corresponding to approximately 80% of the average adiabatic energy loss for non-penetrative scattering. In the adiabatic limit, this suggests a way of determining the approximate average energy loss of non-penetratively scattered H-atoms from the integral energy loss spectrum of all scattered H-atoms. The AIMDEFp calculations predict that in each case the lowest energy loss peak should show additional energy loss in the

  7. Ab initio molecular dynamics calculations on scattering of hyperthermal H atoms from Cu(111) and Au(111)

    SciTech Connect

    Kroes, Geert-Jan Pavanello, Michele; Blanco-Rey, María; Alducin, Maite

    2014-08-07

    Energy loss from the translational motion of an atom or molecule impinging on a metal surface to the surface may determine whether the incident particle can trap on the surface, and whether it has enough energy left to react with another molecule present at the surface. Although this is relevant to heterogeneous catalysis, the relative extent to which energy loss of hot atoms takes place to phonons or electron-hole pair (ehp) excitation, and its dependence on the system's parameters, remain largely unknown. We address these questions for two systems that present an extreme case of the mass ratio of the incident atom to the surface atom, i.e., H + Cu(111) and H + Au(111), by presenting adiabatic ab initio molecular dynamics (AIMD) predictions of the energy loss and angular distributions for an incidence energy of 5 eV. The results are compared to the results of AIMDEFp calculations modeling energy loss to ehp excitation using an electronic friction (“EF”) model applied to the AIMD trajectories, so that the energy loss to the electrons is calculated “post” (“p”) the computation of the AIMD trajectory. The AIMD calculations predict average energy losses of 0.38 eV for Cu(111) and 0.13-0.14 eV for Au(111) for H-atoms that scatter from these surfaces without penetrating the surface. These energies closely correspond with energy losses predicted with Baule models, which is suggestive of structure scattering. The predicted adiabatic integral energy loss spectra (integrated over all final scattering angles) all display a lowest energy peak at an energy corresponding to approximately 80% of the average adiabatic energy loss for non-penetrative scattering. In the adiabatic limit, this suggests a way of determining the approximate average energy loss of non-penetratively scattered H-atoms from the integral energy loss spectrum of all scattered H-atoms. The AIMDEFp calculations predict that in each case the lowest energy loss peak should show additional energy loss

  8. Ab initio molecular dynamics calculations on scattering of hyperthermal H atoms from Cu(111) and Au(111)

    NASA Astrophysics Data System (ADS)

    Kroes, Geert-Jan; Pavanello, Michele; Blanco-Rey, María; Alducin, Maite; Auerbach, Daniel J.

    2014-08-01

    Energy loss from the translational motion of an atom or molecule impinging on a metal surface to the surface may determine whether the incident particle can trap on the surface, and whether it has enough energy left to react with another molecule present at the surface. Although this is relevant to heterogeneous catalysis, the relative extent to which energy loss of hot atoms takes place to phonons or electron-hole pair (ehp) excitation, and its dependence on the system's parameters, remain largely unknown. We address these questions for two systems that present an extreme case of the mass ratio of the incident atom to the surface atom, i.e., H + Cu(111) and H + Au(111), by presenting adiabatic ab initio molecular dynamics (AIMD) predictions of the energy loss and angular distributions for an incidence energy of 5 eV. The results are compared to the results of AIMDEFp calculations modeling energy loss to ehp excitation using an electronic friction ("EF") model applied to the AIMD trajectories, so that the energy loss to the electrons is calculated "post" ("p") the computation of the AIMD trajectory. The AIMD calculations predict average energy losses of 0.38 eV for Cu(111) and 0.13-0.14 eV for Au(111) for H-atoms that scatter from these surfaces without penetrating the surface. These energies closely correspond with energy losses predicted with Baule models, which is suggestive of structure scattering. The predicted adiabatic integral energy loss spectra (integrated over all final scattering angles) all display a lowest energy peak at an energy corresponding to approximately 80% of the average adiabatic energy loss for non-penetrative scattering. In the adiabatic limit, this suggests a way of determining the approximate average energy loss of non-penetratively scattered H-atoms from the integral energy loss spectrum of all scattered H-atoms. The AIMDEFp calculations predict that in each case the lowest energy loss peak should show additional energy loss in the

  9. Characterization of one-dimensional molecular chains of 4,4′-biphenyl diisocyanide on Au(111) by scanning tunneling microscopy

    SciTech Connect

    Zhou, Jing; Li, Yan; Zahl, Percy; Sutter, Peter; Stacchiola, Dario J.; White, Michael G.

    2015-03-14

    The morphology and electronic structure of vapor deposited 4,4′-biphenyldiisocyanide (BPDI) on a Au(111) surface were investigated using variable-temperature scanning tunneling microscopy. When deposited at room temperature, BPDI molecules form one-dimensional molecular chains similar to that recently observed for the structurally related 1,4-phenyl diisocyanide (PDI). Compared to PDI, the longer periodicity for the BPDI molecular chains is consistent with the addition of a second phenyl ring and supports a structural model in which the BPDI molecules lie parallel to the surface and interconnected by Au-adatoms. The molecular chains are mostly aligned along the [11{sup -}0] direction of the Au(111) substrate, but exhibit frequent changes in angle that are consistent with directions between fcc and hcp three-fold hollow sites. Dispersion-corrected density functional theory calculations for one-dimensional chains of BPDI molecules bound end-to-end via their isocyanide groups to Au-adatoms reproduce the observed periodicity of the chains and show that this morphology is energetically favored over upright binding with one free —NC group. The spatially resolved conductance (dI/dV) map for BPDI on Au(111) exhibits a feature centered at −0.67 eV below the Fermi level which are delocalized along the chain with maxima at the Au-adatom and biphenyl positions. This occupied resonant feature is close to that previously observed for the PDI in both photoemission and conductance measurements and is attributed to an occupied interfacial state resulting from BPDI-Au interactions.

  10. Adsorption of the ionic liquid [BMP][TFSA] on Au(111) and Ag(111): substrate effects on the structure formation investigated by STM.

    PubMed

    Uhl, Benedikt; Buchner, Florian; Alwast, Dorothea; Wagner, Nadja; Behm, R Jürgen

    2013-01-01

    In order to resolve substrate effects on the adlayer structure and structure formation and on the substrate-adsorbate and adsorbate-adsorbate interactions, we investigated the adsorption of thin films of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium-bis(trifluoromethylsulfonyl)imide [BMP][TFSA] on the close-packed Ag(111) and Au(111) surfaces by scanning tunneling microscopy, under ultra high vacuum (UHV) conditions in the temperature range between about 100 K and 293 K. At room temperature, highly mobile 2D liquid adsorbate phases were observed on both surfaces. At low temperatures, around 100 K, different adsorbed IL phases were found to coexist on these surfaces, both on silver and gold: a long-range ordered ('2D crystalline') phase and a short-range ordered ('2D glass') phase. Both phases exhibit different characteristics on the two surfaces. On Au(111), the surface reconstruction plays a major role in the structure formation of the 2D crystalline phase. In combination with recent density functional theory calculations, the sub-molecularly resolved STM images allow to clearly discriminate between the [BMP](+) cation and [TFSA](-) anion. PMID:24367760

  11. Microcantilever-based sensors: effect of morphology, adhesion, and cleanliness of the sensing surface on surface stress.

    PubMed

    Tabard-Cossa, Vincent; Godin, Michel; Burgess, Ian J; Monga, Tanya; Lennox, R Bruce; Grütter, Peter

    2007-11-01

    The surface stress response of micromechanical cantilever-based sensors was studied as a function of the morphology, adhesion, and cleanliness of the gold sensing surface. Two model systems were investigated: the adsorption of alkanethiol self-assembled monolayers at the gas-solid interface and the potential-controlled adsorption of anions at the liquid-solid interface. The potential-induced surface stress, on a smooth and continuous polycrystalline Au(111)-textured microcantilever in 0.1 M HClO4, is in excellent agreement with macroscopic Au(111) single-crystal electrode results. It is shown that ambient contaminants on the sensing surface dramatically alter the surface stress-potential response. This observation can be misinterpreted as evidence that for polycrystalline Au(111) microcantilever electrodes, surface stress is dominated by surface energy change. Results for anions adsorption on gold are in contrast to the gas-phase model system. We demonstrate that the average grain size of the gold sensing surface strongly influences the magnitude of the surface stress change induced by the adsorption of octanethiol. A 25-fold amplification of the change in surface stress is observed on increasing the average gold grain size of the sensing surface from 90 to 500 nm.

  12. Sulfur dimers adsorbed on Au(111) as building blocks for sulfur octomers formation: A density functional study

    SciTech Connect

    Hernandez-Tamargo, Carlos E.; Montero-Alejo, Ana Lilian; Pujals, Daniel Codorniu; Mikosch, Hans

    2014-07-28

    Experimental scanning tunneling microscopy (STM) studies have shown for more than two decades rectangular formations when sulfur atoms are deposited on Au(111) surfaces. The precursors have ranged from simple molecules or ions, such as SO{sub 2} gas or sulfide anions, to more complex organosulfur compounds. We investigated, within the framework of the Density Functional Theory, the structure of these rectangular patterns assuming them entirely composed of sulfur atoms as the experimental evidence suggests. The sulfur coverage at which the simulations were carried out (0.67 ML or higher) provoked that the sulfur-sulfur association had to be taken into account for achieving a good agreement between the sets of simulated and experimental STM images. A combination of four sulfur dimers per rectangular formation properly explained the trends obtained by the experimental STM analysis which were related with the rectangles' size and shape fluctuations together with sulfur-sulfur distances within these rectangles. Finally, a projected density of states analysis showed that the dimers were capable of altering the Au(5d) electronic states at the same level as atomic sulfur adsorbed at low coverage. Besides, sulfur dimers states were perfectly distinguished, whose presence near and above the Fermi level can explain both: sulfur-sulfur bond elongation and dimers stability when they stayed adsorbed on the surface at high coverage.

  13. Surface protected lithium-metal-oxide electrodes

    DOEpatents

    Thackeray, Michael M.; Kang, Sun-Ho

    2016-04-05

    A lithium-metal-oxide positive electrode having a layered or spinel structure for a non-aqueous lithium electrochemical cell and battery is disclosed comprising electrode particles that are protected at the surface from undesirable effects, such as electrolyte oxidation, oxygen loss or dissolution by one or more lithium-metal-polyanionic compounds, such as a lithium-metal-phosphate or a lithium-metal-silicate material that can act as a solid electrolyte at or above the operating potential of the lithium-metal-oxide electrode. The surface protection significantly enhances the surface stability, rate capability and cycling stability of the lithium-metal-oxide electrodes, particularly when charged to high potentials.

  14. Cyanophenyl vs. pyridine substituent: impact on the adlayer structure and formation on HOPG and Au(111).

    PubMed

    Dai, Y; Eggers, B; Metzler, M; Künzel, D; Groß, A; Jacob, T; Ziener, U

    2016-03-01

    A new cyano substituted bis(terpyridine) derivative CN-BTP was synthesized and its adsorption on highly oriented pyrolytic graphite (HOPG) and Au(111) was investigated. CN-BTP is closely related to the previously investigated 2,4'-BTP, where the cyanophenyl groups are replaced by pyridine moieties. The scanning tunneling microscopy (STM) investigation of CN-BTP at the liquid|HOPG interface shows a highly ordered herringbone structure that is stabilized by double weak intermolecular C-HN hydrogen bonds, partially through the -CN substituents, which is different from the most stable square structure of 2,4'-BTP. The adsorption processes were investigated using cyclic voltammetry (CV) on Au(111) in a neutral phosphate buffer. A fast and full adlayer formation could be observed with CN-BTP, whereas an extremely slow process with 2,4'-BTP under the same conditions was found. Our data show that the CN substituents on BTP not only change the structure of the monolayer at the liquid|HOPG interface, but also accelerate the phase transition process in the electrolyte dramatically. This could be explained by the adlayer-substrate interactions, which is supported by DFT calculations. Our findings might be extended more generally to further pyridine comprising self-assembling molecules to fine-tune the adlayer structure and phase transition/adsorption kinetics by replacing pyridine by cyanophenyl moieties.

  15. Two-dimensional TiOx nanostructures on Au(111): a scanning tunneling microscopy and spectroscopy investigation

    NASA Astrophysics Data System (ADS)

    Tumino, F.; Carrozzo, P.; Mascaretti, L.; Casari, C. S.; Passoni, M.; Tosoni, S.; Bottani, C. E.; Li Bassi, A.

    2015-12-01

    We investigated the growth of titanium oxide two-dimensional nanostructures on Au(111), produced by Ti evaporation and post-deposition oxidation. Scanning tunneling microscopy and spectroscopy (STM and STS) and low-energy electron diffraction measurements characterized the morphological, structural and electronic properties of the observed structures. Five distinct TiOx phases were identified: the honeycomb and pinwheel phases appear as monolayer films wetting the gold surface, while nanocrystallites of the triangular, row and needle phases grow mainly over the honeycomb or pinwheel layers. Density Functional Theory investigation of the honeycomb structure supports a (2× 2) structural model based on a Ti-O bilayer having Ti2O3 stoichiometry. The pinwheel phase was observed to evolve, for increasing coverage, from single triangular crystallites to a well-ordered film forming a (4\\sqrt{7}× 4\\sqrt{7})R19.1^\\circ superstructure, which can be interpreted within a moiré-like model. Structural characteristics of the other three phases were disclosed from the analysis of high-resolution STM measurements. STS measurements revealed a partial metallization of honeycomb and pinwheel and a semiconducting character of row and triangular phases.

  16. Electrochemical and in-situ scanning tunneling microscopy studies of bis(fluorosulfonyl)imide and bis(trifluoromethanesulfonyl)imide based ionic liquids on graphite and gold electrodes and lithium salt influence

    NASA Astrophysics Data System (ADS)

    Hu, Xiaoyan; Chen, Chunlei; Yan, Jiawei; Mao, Bingwei

    2015-10-01

    We report electrochemical and in-situ scanning tunneling microscopy (STM) studies of surface processes on graphite and Au(111) electrodes in N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide (Py13FSI) and N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (Py13TFSI) ionic liquids in the absence and presence of LiTFSI salt. In both of neat ionic liquids, the intercalation of cations and exfoliation of HOPG layers occur during cathodic excursion. However, the surface decomposition of FSI anions can form an effective protection film on the surface, which suppresses the intercalation and exfoliation processes, while the surface decomposition of TFSI anions mainly causes etching of the surface, which makes the intercalation and exfoliation easier to proceed. The addition of Li salt can promote the formation of the protective film, especially in Py13FSI, and thus significantly suppress the intercalation and exfoliation processes. The discrepancies between these two ionic liquids are caused by the different anion interactions with graphite. Additionally, comparisons of the behaviors on HOPG and on Au(111) confirm that the surface processes are crucially dependent on the nature of the electrode. Trace amounts of oxygen and water can cause the formation of a film-like structure on Au(111), but show no apparent influence on HOPG.

  17. 21 CFR 870.2370 - Electrocardiograph surface electrode tester.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Electrocardiograph surface electrode tester. 870... Electrocardiograph surface electrode tester. (a) Identification. An electrocardiograph surface electrode tester is a device used to test the function and application of electrocardiograph electrodes. (b)...

  18. 21 CFR 870.2370 - Electrocardiograph surface electrode tester.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Electrocardiograph surface electrode tester. 870... Electrocardiograph surface electrode tester. (a) Identification. An electrocardiograph surface electrode tester is a device used to test the function and application of electrocardiograph electrodes. (b)...

  19. 21 CFR 870.2370 - Electrocardiograph surface electrode tester.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Electrocardiograph surface electrode tester. 870... Electrocardiograph surface electrode tester. (a) Identification. An electrocardiograph surface electrode tester is a device used to test the function and application of electrocardiograph electrodes. (b)...

  20. 21 CFR 870.2370 - Electrocardiograph surface electrode tester.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Electrocardiograph surface electrode tester. 870... Electrocardiograph surface electrode tester. (a) Identification. An electrocardiograph surface electrode tester is a device used to test the function and application of electrocardiograph electrodes. (b)...

  1. 21 CFR 870.2370 - Electrocardiograph surface electrode tester.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Electrocardiograph surface electrode tester. 870... Electrocardiograph surface electrode tester. (a) Identification. An electrocardiograph surface electrode tester is a device used to test the function and application of electrocardiograph electrodes. (b)...

  2. Revisiting the adsorption of copper-phthalocyanine on Au(111) including van der Waals corrections.

    PubMed

    Lüder, Johann; Eriksson, Olle; Sanyal, Biplab; Brena, Barbara

    2014-03-28

    We have studied the adsorption of copper-phthalocyanine on Au(111) by means of van der Waals corrected density functional theory using the Tkatchenko-Scheffler method. We have compared the element and site resolved adsorption distances to recent experimental normal-incident X-ray standing wave measurements. The measured adsorption distances could be reproduced within a deviation of 1% for the Cu atom, 1% for the C atoms, and 2% for the N atoms. The molecule was found to have a magnetic moment of 1 μB distributed over the Cu and the N atoms of the pyrrole ring. Simulated scanning tunnel microscopy images based on the total and on the spin-resolved differential charge densities are provided for bias voltages of -1.45 and 1.45 eV.

  3. Stick–slip behaviour on Au(111) with adsorption of copper and sulfate

    PubMed Central

    Podgaynyy, Nikolay; Wezisla, Sabine; Molls, Christoph; Iqbal, Shahid

    2015-01-01

    Summary Several transitions in the friction coefficient with increasing load are found on Au(111) in sulfuric acid electrolyte containing Cu ions when a monolayer (or submonolayer) of Cu is adsorbed. At the corresponding normal loads, a transition to double or multiple slips in stick–slip friction is observed. The stick length in this case corresponds to multiples of the lattice distance of the adsorbed sulfate, which is adsorbed in a √3 × √7 superstructure on the copper monolayer. Stick–slip behaviour for the copper monolayer as well as for 2/3 coverage can be observed at F N ≥ 15 nN. At this normal load, a change from a small to a large friction coefficient occurs. This leads to the interpretation that the tip penetrates the electrochemical double layer at this point. At the potential (or point) of zero charge (pzc), stick–slip resolution persists at all normal forces investigated. PMID:25977853

  4. Revisiting the adsorption of copper-phthalocyanine on Au(111) including van der Waals corrections

    SciTech Connect

    Lüder, Johann; Eriksson, Olle; Sanyal, Biplab; Brena, Barbara

    2014-03-28

    We have studied the adsorption of copper-phthalocyanine on Au(111) by means of van der Waals corrected density functional theory using the Tkatchenko-Scheffler method. We have compared the element and site resolved adsorption distances to recent experimental normal-incident X-ray standing wave measurements. The measured adsorption distances could be reproduced within a deviation of 1% for the Cu atom, 1% for the C atoms, and 2% for the N atoms. The molecule was found to have a magnetic moment of 1 μ{sub B} distributed over the Cu and the N atoms of the pyrrole ring. Simulated scanning tunnel microscopy images based on the total and on the spin-resolved differential charge densities are provided for bias voltages of −1.45 and 1.45 eV.

  5. Electronic Structure and Luminescence of Quasi-Freestanding MoS2 Nanopatches on Au(111).

    PubMed

    Krane, Nils; Lotze, Christian; Läger, Julia M; Reecht, Gaël; Franke, Katharina J

    2016-08-10

    Monolayers of transition metal dichalcogenides are interesting materials for optoelectronic devices due to their direct electronic band gaps in the visible spectral range. Here, we grow single layers of MoS2 on Au(111) and find that nanometer-sized patches exhibit an electronic structure similar to their freestanding analogue. We ascribe the electronic decoupling from the Au substrate to the incorporation of vacancy islands underneath the intact MoS2 layer. Excitation of the patches by electrons from the tip of a scanning tunneling microscope leads to luminescence of the MoS2 junction and reflects the one-electron band structure of the quasi-freestanding layer. PMID:27459588

  6. Revisiting the adsorption of copper-phthalocyanine on Au(111) including van der Waals corrections.

    PubMed

    Lüder, Johann; Eriksson, Olle; Sanyal, Biplab; Brena, Barbara

    2014-03-28

    We have studied the adsorption of copper-phthalocyanine on Au(111) by means of van der Waals corrected density functional theory using the Tkatchenko-Scheffler method. We have compared the element and site resolved adsorption distances to recent experimental normal-incident X-ray standing wave measurements. The measured adsorption distances could be reproduced within a deviation of 1% for the Cu atom, 1% for the C atoms, and 2% for the N atoms. The molecule was found to have a magnetic moment of 1 μB distributed over the Cu and the N atoms of the pyrrole ring. Simulated scanning tunnel microscopy images based on the total and on the spin-resolved differential charge densities are provided for bias voltages of -1.45 and 1.45 eV. PMID:24697474

  7. Imaging the Bonds of Dehalogenated Benzene Radicals on Cu(111) and Au(111).

    PubMed

    Simic-Milosevic, Violeta; Mehlhorn, Michael; Morgenstern, Karina

    2016-09-01

    Dissociative adsorption of doubly substituted benzene molecules leads to formation of benzyne radicals. In this study, co-adsorbed hydrogen molecules are used in scanning tunneling hydrogen microscopy to enhance the contrast of the meta- and the para-isomers of these radicals on Cu(111) and Au(111). Up to three hydrogen molecules are attached to one radical. One hydrogen molecule reveals the orientation of the carbon ring and its adsorption site, allowing discrimination between the two radicals. Two hydrogen molecules reflect the bond picture of the carbon skeleton and reveals that adsorption on Cu(111) distorts the meta- isomer differently from its gas-phase distortion. Three hydrogen molecules allow us to determine the bond picture of a minor species.

  8. Electronic Structure and Luminescence of Quasi-Freestanding MoS2 Nanopatches on Au(111)

    PubMed Central

    2016-01-01

    Monolayers of transition metal dichalcogenides are interesting materials for optoelectronic devices due to their direct electronic band gaps in the visible spectral range. Here, we grow single layers of MoS2 on Au(111) and find that nanometer-sized patches exhibit an electronic structure similar to their freestanding analogue. We ascribe the electronic decoupling from the Au substrate to the incorporation of vacancy islands underneath the intact MoS2 layer. Excitation of the patches by electrons from the tip of a scanning tunneling microscope leads to luminescence of the MoS2 junction and reflects the one-electron band structure of the quasi-freestanding layer. PMID:27459588

  9. State-to-state time-of-flight measurements of NO scattering from Au(111): direct observation of translation-to-vibration coupling in electronically nonadiabatic energy transfer.

    PubMed

    Golibrzuch, Kai; Shirhatti, Pranav R; Altschäffel, Jan; Rahinov, Igor; Auerbach, Daniel J; Wodtke, Alec M; Bartels, Christof

    2013-09-12

    Translational motion is believed to be a spectator degree of freedom in electronically nonadiabatic vibrational energy transfer between molecules and metal surfaces, but the experimental evidence available to support this view is limited. In this work, we have experimentally determined the translational inelasticity in collisions of NO molecules with a single-crystal Au(111) surface-a system with strong electronic nonadiabaticity. State-to-state molecular beam surface scattering was combined with an IR-UV double resonance scheme to obtain high-resolution time-of-flight data. The measurements include vibrationally elastic collisions (v = 3→3, 2→2) as well as collisions where one or two quanta of molecular vibration are excited (2→3, 2→4) or de-excited (2→1, 3→2, 3→1). In addition, we have carried out comprehensive measurements of the effects of rotational excitation on the translational energy of the scattered molecules. We find that under all conditions of this work, the NO molecules lose a large fraction (∼0.45) of their incidence translational energy to the surface. Those molecules that undergo vibrational excitation (relaxation) during the collision recoil slightly slower (faster) than vibrationally elastically scattered molecules. The amount of translational energy change depends on the surface temperature. The translation-to-rotation coupling, which is well-known for v = 0→0 collisions, is found to be significantly weaker for vibrationally inelastic than elastic channels. Our results clearly show that the spectator view of the translational motion in electronically nonadiabatic vibrational energy transfer between NO and Au(111) is only approximately correct.

  10. Identification of Non-Faradaic Processes by Measurement of the Electrochemical Peltier Heat during the Silver Underpotential Deposition on Au(111).

    PubMed

    Frittmann, Stefan; Halka, Vadym; Schuster, Rolf

    2016-04-01

    We measured the heat which is reversibly exchanged during the course of an electrochemical surface reaction, i.e., the deposition/dissolution of the first two monolayers of Ag on a Au(111) surface in (bi)sulfate and perchlorate containing electrolytes. The reversibly exchanged heat corresponds to the Peltier heat of the reaction and is linearly related to its entropy change, including also non-Faradaic side processes. Hence, the measurement of the Peltier heat provides thermodynamic information on the electrochemical processes which is complementary to the current-potential relations usually obtained by conventional electrochemical methods. From the variation of the molar Peltier heat during the various stages of the deposition reaction we inferred that co-adsorption processes of anions and Ag do not play a prominent role, while we find strong indications for a charge neutral substitution reaction of adsorbed anions by hydroxide, which would not show up in cyclic voltammetry. PMID:26916206

  11. Potential-dependent structures investigated at the perchloric acid solution/iodine modified Au(111) interface by electrochemical frequency-modulation atomic force microscopy.

    PubMed

    Utsunomiya, Toru; Tatsumi, Shoko; Yokota, Yasuyuki; Fukui, Ken-ichi

    2015-05-21

    Electrochemical frequency-modulation atomic force microscopy (EC-FM-AFM) was adopted to analyze the electrified interface between an iodine modified Au(111) and a perchloric acid solution. Atomic resolution imaging of the electrode was strongly dependent on the electrode potential within the electrochemical window: each iodine atom was imaged in the cathodic range of the electrode potential, but not in the more anodic range where the tip is retracted by approximately 0.1 nm compared to the cathodic case for the same imaging parameters. The frequency shift versus tip-to-sample distance curves obtained in the electric double layer region on the iodine adlayer indicated that the water structuring became weaker at the anodic potential, where the atomic resolution images could not be obtained, and immediately recovered at the original cathodic potential. The reversible hydration structures were consistent with the reversible topographic images and the cyclic voltammetry results. These results indicate that perchlorate anions concentrated at the anodic potential affect the interface hydration without any irreversible changes to the interface under these conditions.

  12. Ammonia adsorption on iron phthalocyanine on Au(111): Influence on adsorbate-substrate coupling and molecular spin

    SciTech Connect

    Isvoranu, Cristina; Ataman, Evren; Knudsen, Jan; Andersen, Jesper N.; Schnadt, Joachim; Wang Bin; Bocquet, Marie-Laure; Schulte, Karina

    2011-03-21

    The adsorption of ammonia on Au(111)-supported monolayers of iron phthalocyanine has been investigated by x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, and density functional theory calculations. The ammonia-induced changes of the x-ray photoemission lines show that a dative bond is formed between ammonia and the iron center of the phthalocyanine molecules, and that the local spin on the iron atom is quenched. This is confirmed by density functional theory, which also shows that the bond between the iron center of the metalorganic complex and the Au(111) substrate is weakened upon adsorption of ammonia. The experimental results further show that additional adsorption sites exist for ammonia on the iron phthalocyanine monolayer.

  13. Chiral morphologies and interfacial electronic structure of naphtho[2,3-a]pyrene on Au(111).

    PubMed

    France, C B; Parkinson, B A

    2004-03-30

    The adsorption of the two-dimensionally chiral naphtho[2,3-a]pyrene molecule has been studied on Au(111). Both structural and electronic properties of the naphtho[2,3-a]pyrene (NP)/Au(111) interface have been measured. Ultraviolet and X-ray photoelectron spectroscopy have been employed to measure the energies of the molecular orbitals of the NP film with respect to the gold Fermi level. A Schottky junction with a large interface dipole (0.99 eV) is formed between Au(111) and NP. Temperature-programmed desorption was used to determine that adsorbed NP has a binding energy of 102.2 kJ/mol. Chiral domains have been observed with scanning tunneling microscopy due to the spontaneous phase separation of the 2-D enantiomers. Two distinct structural polymorphs have been observed, one of which has homochiral paired molecular rows. Models of the 2D structure are proposed that are in excellent agreement with experimental measurements.

  14. Oxide modified air electrode surface for high temperature electrochemical cells

    DOEpatents

    Singh, Prabhakar; Ruka, Roswell J.

    1992-01-01

    An electrochemical cell is made having a porous cermet electrode (16) and a porous lanthanum manganite electrode (14), with solid oxide electrolyte (15) between them, where the lanthanum manganite surface next to the electrolyte contains a thin discontinuous layer of high surface area cerium oxide and/or praseodymium oxide, preferably as discrete particles (30) in contact with the air electrode and electrolyte.

  15. Experimental investigation of a thermionic converter with developed surface electrodes

    SciTech Connect

    Luke, J.R.; El-Genk, M.S.; Adrian, J.M.

    1997-01-01

    A thermionic converter with developed planar electrode surfaces is designed and tested. One of the electrodes has concentric circular grooves cut into its surface, while the other electrode surface is smooth. The grooves are 0.5 mm deep and 0.5 mm wide, having lands that are 1.0 mm wide. The experimental setup is flexible so that either the smooth or developed surface electrode can be operated as the emitter, with the other operating as the collector. The I-V characteristics and power output are compared for the two electrode arrangements. {copyright} {ital 1997 American Institute of Physics.}

  16. Surface Plasma Source Electrode Activation by Surface Impurities

    SciTech Connect

    Dudnikov, Vadim; Johnson, Rolland P.; Han, B.; Murray, S. N.; Pennisi, T. R.; Santana, M.; Stockli, Martin P.; Welton, R. F.

    2011-09-26

    In experiments with RF saddle antenna surface plasma sources (SPS), the efficiency of H{sup -} ion generation was increased by up to a factor of 5 by plasma electrode 'activation', without supplying additional Cs, by heating the collar to high temperature for several hours using hot air flow and plasma discharge. Without cracking or heating the cesium ampoule, but likely with Cs recovery from impurities, the achieved energy efficiency was comparable to that of conventionally cesiated SNS RF sources with an external or internal Cs supply. In the experiments, optimum cesiation was produced (without additional Cs) by the collection and trapping of traces of remnant cesium compounds from SPS surfaces. Such activation by accumulation of impurities on electrode surfaces can be a reason for H{sup -} emission enhancement in other so-called 'volume' negative ion sources.

  17. Surface Plasma Source Electrode Activation by Surface Impurities

    SciTech Connect

    Dudnikov, Vadim; Han, Baoxi; Johnson, Rolland P.; Murray Jr, S N; Pennisi, Terry R; Santana, Manuel; Stockli, Martin P; Welton, Robert F

    2011-01-01

    In experiments with RF saddle antenna surface plasma sources (SPS), the efficiency of H- ion generation was increased by up to a factor of 5 by long time plasma electrode activation, without adding Cs from Cs supply, by heating the collar to high temperature using hot air flow and plasma discharge. Without cracking or heating the cesium ampoule, but likely with Cs recovery from impurities, the achieved energy efficiency was comparable to that of conventionally cesiated SNS RF sources with an external or internal Cs supply. In the experiments, perfect cesiation was produced (without additional Cs supply) by the collection and trapping of traces of remnant cesium compounds from SPS surfaces.

  18. LEED I/V determination of the structure of a MoO3 monolayer on Au(111): Testing the performance of the CMA-ES evolutionary strategy algorithm, differential evolution, a genetic algorithm and tensor LEED based structural optimization

    NASA Astrophysics Data System (ADS)

    Primorac, E.; Kuhlenbeck, H.; Freund, H.-J.

    2016-07-01

    The structure of a thin MoO3 layer on Au(111) with a c(4 × 2) superstructure was studied with LEED I/V analysis. As proposed previously (Quek et al., Surf. Sci. 577 (2005) L71), the atomic structure of the layer is similar to that of a MoO3 single layer as found in regular α-MoO3. The layer on Au(111) has a glide plane parallel to the short unit vector of the c(4 × 2) unit cell and the molybdenum atoms are bridge-bonded to two surface gold atoms with the structure of the gold surface being slightly distorted. The structural refinement of the structure was performed with the CMA-ES evolutionary strategy algorithm which could reach a Pendry R-factor of ∼ 0.044. In the second part the performance of CMA-ES is compared with that of the differential evolution method, a genetic algorithm and the Powell optimization algorithm employing I/V curves calculated with tensor LEED.

  19. IN SITU SURFACE X-RAY SCATTERING STUDIES OF ELECTROSORPTION

    SciTech Connect

    WANG,J.X.; ADZIC,R.R.; OCKO,B.M.

    1998-07-01

    A short review of the application of surface x-ray scattering techniques to the electrode/electrolyte interfaces is presented. Recent results on metal, halide, and metal-halide adlayers with three specific systems: Bi on Au(100) and Au(110); Br on Au(100) and Ag(100); and the coadsorption of Tl with Br or I on Au(111), are given as an illustration. Factors affecting ordering of pure metal and halide adlayers and the metal-halide surface compounds are discussed in some detail.

  20. High resolution electrochemical STM : new structural results for underpotentially deposited Cu on Au(111) in acid sulfate solution.

    SciTech Connect

    Sieradzki, Karl; Vasiljevic, Natasa; Viyannalage, L.K.T.; Dimitrov, Nikolay

    2007-09-01

    Adsorption of sulfate assists Cu monolayer underpotential deposition (upd) on Au(111) in a unique way, rendering two distinct structural stages: (i) formation of a low-density Cu phase at coverage of 2/3 ML known as the ({radical}3 x {radical}3) R30{sup o} or honeycomb phase; (ii) formation of a complete monolayer, i.e., Cu-(1 x 1) phase pseudomorphic with respect to underlying Au(111) substrate. In this paper we present new structural in situ scanning tunneling microscopy (STM) results for this system. We show and discuss the STM imaging of the copper honeycomb superstructure probed underneath the co-adsorbed ({radical}3 x {radical}3)R30{sup o} sulfate adlayer in the low-density phase. High resolution imaging during the phase transition from the low to high density copper phase unambiguously shows the existence of an ordered sulfate structure p(2 x 2) on the pseudomorphic Cu-(1 x 1) layer. The new structure is seen during the co-existence of two copper phases as well as upon completion of the Cu-(1 x 1) monolayer. While supported by earlier chronocoulometric measurements in the same system, the new structural results raise questions that need to be addressed in a future work.

  1. Structure and Electronic Properties of Polymer Chains and Graphene Nanoribbon Formed by Molecular Self-Assembly on Au(111)

    NASA Astrophysics Data System (ADS)

    Ma, Chuanxu; Fuentes-Cabrera, Miguel A.; Sumpter, Bobby G.; Hong, Kunlun; Li, An-Ping; Xiao, Zhongcan; Lu, Wenchang; Bernholc, J.

    Graphene nanoribbons (GNRs) with bandgaps are promising building blocks for ultra-fast electronics. Bottom-up synthesis of GNRs from aromatic hydrocarbon molecules has been proven to be an effective way to control GNR's width with atomically precise edge structures. Using scanning tunneling microscopy (STM), we study the formation of both linear polymer chains and narrow GNRs in the bottom-up self-assembly process with the DBBA molecules as the precursor on Au(111). The linear polymer chains are formed after the deposition of DBBA and 200 °C annealing for 30 min. The polymers can be converted to 7-AGNRs (seven-carbon wide armchair GNRs) after 400 °C annealing. Interestingly, second-layer polymer is seen to survive on the GNRs during the annealing process. This result indicates that the Au(111) substrate plays an important role in the dehydrogenation process and the formation of GNRs, which is confirmed by our DFT calculations. Electronically, the polymers show a bandgap of 3.4 eV, much larger than that of GNRs. After annealing at 500 °C for 30 min, wider GNRs can form: 14-AGNR, 21-AGNR. The 7-AGNR shows a typical edge state at -1.1 eV, while for 14-AGNR it is at -1.35 eV. Moreover, junctions of GNRs with different widths can be formed with pronounced boundary states.

  2. Influence of molecular ordering on electrical and friction properties of omega-(trans-4-stilbene)alkylthiol self-assembled monolayers on Au (111)

    SciTech Connect

    Qi, Yabing; Liu, Xiaosong; Hendriksen, B.L.M.; Navarro, V.; Park, Jeong Y.; Ratera, Imma; Klopp, J.M.; Edder, C.; Himpsel, Franz J.; Frechet, J.M.J.; Haller, Eugene E.; Salmeron, Miquel

    2010-04-21

    The electrical and friction properties of omega-(trans-4-stilbene)alkylthiol self-assembled monolayers (SAMs) on Au(111) were investigated using atomic force microscopy (AFM) and near edge x-ray absorption fine structure spectroscopy (NEXAFS). The sample surface was uniformly covered with a molecular film consisting of very small grains. Well-ordered and flat monolayer islands were formed after the sample was heated in nitrogen at 120 oC for 1 h. While lattice resolved AFM images revealed a crystalline phase in the islands, the area between islands showed no order. The islands exhibit substantial reduction (50percent) in friction, supporting the existence of good ordering. NEXAFS measurements revealed an average upright molecular orientation in the film, both before and after heating, with a narrower tilt-angle distribution for the heated fim. Conductance-AFM measurements revealed a two orders of magnitude higher conductivity on the ordered islands than on the disordered phase. We propose that the conductance enhancement is a result of a better pi-pi stacking between the trans-stilbene molecular units as a result of improved ordering in islands.

  3. Individual finger classification from surface EMG: Influence of electrode set.

    PubMed

    Celadon, Nicolo; Dosen, Strahinja; Paleari, Marco; Farina, Dario; Ariano, Paolo

    2015-01-01

    The aim of this work was to minimize the number of channels, determining acceptable electrode locations and optimizing electrode-recording configurations to decode isometric flexion and extension of individual fingers. Nine healthy subjects performed cyclical isometric contractions activating individual fingers. During the experiment they tracked a moving visual marker indicating the contraction type (flexion/extension), desired activation level and the finger that should be employed. Surface electromyography (sEMG) signals were detected from the forearm muscles using a matrix of 192 channels (24 longitudinal columns and 8 transversal rows, 10 mm inter-electrode distance). The classification was evaluated in the context of a linear discriminant analysis (LDA) with different sets of EMG electrodes: A) one linear array of 8 electrodes, B) two arrays of 8 electrodes each, C) a set with one electrode on the barycenter of each sEMG activity area, D) all the recorded channels. The results showed that the classification accuracy depended on the electrode set (F=14.67, p<;0.001). The best reduction approaches were the barycenter calculation and the use of two linear arrays of electrodes, which performed similarly to each other (both > 82% of average success rate). Considering the computation time and electrode positioning, it is concluded that two arrays of 8 electrodes provide an optimal configuration to classify the isometric flexion and extension of individual fingers.

  4. Surface modification of active material structures in battery electrodes

    DOEpatents

    Erickson, Michael; Tikhonov, Konstantin

    2016-02-02

    Provided herein are methods of processing electrode active material structures for use in electrochemical cells or, more specifically, methods of forming surface layers on these structures. The structures are combined with a liquid to form a mixture. The mixture includes a surface reagent that chemically reacts and forms a surface layer covalently bound to the structures. The surface reagent may be a part of the initial liquid or added to the mixture after the liquid is combined with the structures. In some embodiments, the mixture may be processed to form a powder containing the structures with the surface layer thereon. Alternatively, the mixture may be deposited onto a current collecting substrate and dried to form an electrode layer. Furthermore, the liquid may be an electrolyte containing the surface reagent and a salt. The liquid soaks the previously arranged electrodes in order to contact the structures with the surface reagent.

  5. Diaphragmatic activity induced by cortical stimulation: surface versus esophageal electrodes.

    PubMed

    Gea, J; Espadaler, J M; Guiu, R; Aran, X; Seoane, L; Broquetas, J M

    1993-02-01

    Evoked responses of the diaphragm can be induced by magnetic cortical stimulation and recorded by either surface or esophageal electrodes. The former recording system is tolerated better by the patient but has potential problems with the specificity of the diaphragmatic signal. This study compares the responses of the diaphragm to cortical stimulation that were recorded simultaneously with surface and esophageal electrodes on seven patients (61 +/- 4 yr) with chronic obstructive pulmonary diseases. Stimuli were delivered in three ventilatory conditions: at baseline, during deep breathing, and during voluntary panting. No differences were observed between results recorded by surface and esophageal electrodes [amplitude of the compound motor of the action potential (CMAP), 0.8 +/- 0.1 vs. 0.8 +/- 0.1 mV, NS; latency, 13.1 +/- 0.4 vs. 12.6 +/- 0.5 ms, NS]. In addition, significant correlations were found (CMAP, r = 0.77, P < 0.001; latency, r = 0.71, P = 0.002). The concordance analysis, however, indicated some dissimilarity between the recordings of the electrodes (CMAP, R1 = 0.31; latency, R1 = 0.26). These differences may be due to the area of the muscle mainly recorded by each electrode and/or to the additional activity from other muscles recorded by surface electrodes. On the other hand, the diaphragmatic responses observed in these patients with chronic obstructive pulmonary diseases were similar to those previously reported in healthy subjects. PMID:8458780

  6. Chemical and morphological characteristics of lithium electrode surfaces

    NASA Technical Reports Server (NTRS)

    Yen, S. P. S.; Shen, D.; Vasquez, R. P.; Grunthaner, F. J.; Somoano, R. B.

    1981-01-01

    Lithium electrode surfaces were analyzed for chemical and morphological characteristics, using electron spectroscopy chemical analysis (ESCA) and scanning electron microscopy (SEM). Samples included lithium metal and lithium electrodes which were cycled in a 1.5 M lithium arsenic hexafluoride/two-methyl tetrahydrofuran electrolyte. Results show that the surface of the as-received lithium metal was already covered by a film composed of LiO2 and an Li2O/CO2 adduct with a thickness of approximately 100-200 A. No evidence of Ni3 was found. Upon exposure of the lithium electrode to a 1.5 M LiAsF6/2-Me-THF electrochemical environment, a second film was observed to form on the surface, consisting primarily of As, Si, and F, possibly in the form of lithium arsenic oxyfluorides or lithium fluorosilicates. It is suggested that the film formation may be attributed to salt degradation.

  7. Field-free junctions for surface electrode ion traps

    NASA Astrophysics Data System (ADS)

    Jordens, Robert; Schmied, R.; Blain, M. G.; Leibfried, D.; Wineland, D.

    2015-05-01

    Intersections between transport guides in a network of RF ion traps are a key ingredient to many implementations of scalable quantum information processing with trapped ions. Several junction architectures demonstrated so far are limited by varying radial secular frequencies, a reduced trap depth, or a non-vanishing RF field along the transport channel. We report on the design and progress in implementing a configurable microfabricated surface electrode Y-junction that employs switchable RF electrodes. An essentially RF-field-free pseudopotential guide between any two legs of the junction can be established by applying RF potential to a suitable pair of electrodes. The transport channel's height above the electrodes, its depth and radial curvature are constant to within 15%. Supported by IARPA, Sandia, NSA, ONR, and the NIST Quantum Information Program.

  8. Changes in the adsorbate dipole layer with changing d-filling of the metal (II) (Co, Ni, Cu) phthalocyanines on Au(111).

    PubMed

    Xiao, Jie; Dowben, Peter A

    2009-02-01

    In combined photoemission and inverse photoemission spectroscopy studies, we observe changes in the metal phthalocyanine molecular orbital offsets with respect to the conducting gold substrate Fermi level, with the changing d-electron filling of the metal (II) (Co, Ni, Cu) phthalocyanines. The implication is that the interfacial dipole layer depends upon the choice of metal (Co, Ni, Cu) centers within the metal (II) phthalocyanines adsorbed on Au(111).

  9. Potential applications of a small high-surface-area platinum electrode as an implanted impedance biosensor or recording electrode

    NASA Astrophysics Data System (ADS)

    Duan, Yvonne Y.; Millard, Rodney E.; Tykocinski, Michael; Lui, Xuguang; Clark, Graeme M.; Cowan, Robert S. C.

    2001-03-01

    A small Platinum (Pt) electrode (geometric area: ~0.43 mm2) was treated in an electrochemical etching process, to produce a highly porous columnar thin layer (~600 nm) on the surface of the electrode. The modified Pt electrode (Pt-p) showed similar electrical properties to a platinum-black electrode but with high mechanical integrity. Previous studies of chronic stimulation had also shown good biocompatibility and surface stability over several months implantation. This paper discusses the potential applications of the modified electrode as an implanted bio-sensor: (1) as a recording electrode compared to an untreated Pt electrode. (2) as a probe in detecting electrical characteristics of living biological material adjacent to the electrode in vivo, which may correlate to inflammation or trauma repair. Results of electrochemical impedance spectroscopy (EIS) revealed much lower electrode interface polarisation impedance, reduced overall electrode impedance, and a largely constant impedance above 100 Hz for the Pt-p electrode compared with untreated Pt electrodes. This provides a platform for recording biological events with low noise interference. Results of A.C. impedance spectroscopy of the high surface area electrode only reflect changes in the surrounding biological environment in the frequency range (1 k Hz to 100 k Hz), interference from electrode polarisation impedance can be neglected. The results imply that the surface-modified electrode is a good candidate for application to implantable biosensors for detecting bio-electric events. The modification procedure and its high surface area concept could have application to a smart MEMS device or microelectrode.

  10. Probing and mapping electrode surfaces in solid oxide fuel cells.

    PubMed

    Blinn, Kevin S; Li, Xiaxi; Liu, Mingfei; Bottomley, Lawrence A; Liu, Meilin

    2012-09-20

    Solid oxide fuel cells (SOFCs) are potentially the most efficient and cost-effective solution to utilization of a wide variety of fuels beyond hydrogen (1-7). The performance of SOFCs and the rates of many chemical and energy transformation processes in energy storage and conversion devices in general are limited primarily by charge and mass transfer along electrode surfaces and across interfaces. Unfortunately, the mechanistic understanding of these processes is still lacking, due largely to the difficulty of characterizing these processes under in situ conditions. This knowledge gap is a chief obstacle to SOFC commercialization. The development of tools for probing and mapping surface chemistries relevant to electrode reactions is vital to unraveling the mechanisms of surface processes and to achieving rational design of new electrode materials for more efficient energy storage and conversion(2). Among the relatively few in situ surface analysis methods, Raman spectroscopy can be performed even with high temperatures and harsh atmospheres, making it ideal for characterizing chemical processes relevant to SOFC anode performance and degradation(8-12). It can also be used alongside electrochemical measurements, potentially allowing direct correlation of electrochemistry to surface chemistry in an operating cell. Proper in situ Raman mapping measurements would be useful for pin-pointing important anode reaction mechanisms because of its sensitivity to the relevant species, including anode performance degradation through carbon deposition(8, 10, 13, 14) ("coking") and sulfur poisoning(11, 15) and the manner in which surface modifications stave off this degradation(16). The current work demonstrates significant progress towards this capability. In addition, the family of scanning probe microscopy (SPM) techniques provides a special approach to interrogate the electrode surface with nanoscale resolution. Besides the surface topography that is routinely collected by AFM

  11. Probing and Mapping Electrode Surfaces in Solid Oxide Fuel Cells

    PubMed Central

    Blinn, Kevin S.; Li, Xiaxi; Liu, Mingfei; Bottomley, Lawrence A.; Liu, Meilin

    2012-01-01

    Solid oxide fuel cells (SOFCs) are potentially the most efficient and cost-effective solution to utilization of a wide variety of fuels beyond hydrogen 1-7. The performance of SOFCs and the rates of many chemical and energy transformation processes in energy storage and conversion devices in general are limited primarily by charge and mass transfer along electrode surfaces and across interfaces. Unfortunately, the mechanistic understanding of these processes is still lacking, due largely to the difficulty of characterizing these processes under in situ conditions. This knowledge gap is a chief obstacle to SOFC commercialization. The development of tools for probing and mapping surface chemistries relevant to electrode reactions is vital to unraveling the mechanisms of surface processes and to achieving rational design of new electrode materials for more efficient energy storage and conversion2. Among the relatively few in situ surface analysis methods, Raman spectroscopy can be performed even with high temperatures and harsh atmospheres, making it ideal for characterizing chemical processes relevant to SOFC anode performance and degradation8-12. It can also be used alongside electrochemical measurements, potentially allowing direct correlation of electrochemistry to surface chemistry in an operating cell. Proper in situ Raman mapping measurements would be useful for pin-pointing important anode reaction mechanisms because of its sensitivity to the relevant species, including anode performance degradation through carbon deposition8, 10, 13, 14 ("coking") and sulfur poisoning11, 15 and the manner in which surface modifications stave off this degradation16. The current work demonstrates significant progress towards this capability. In addition, the family of scanning probe microscopy (SPM) techniques provides a special approach to interrogate the electrode surface with nanoscale resolution. Besides the surface topography that is routinely collected by AFM and STM

  12. Surface Analysis of 4-Aminothiophenol Adsorption at Polycrystalline Platinum Electrodes

    NASA Technical Reports Server (NTRS)

    Rosario-Castro, Belinda I.; Fachini, Estevao R.; Contes, Enid J.; Perez-Davis, Marla E.; Cabrera, Carlos R.

    2008-01-01

    Formation of self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) on polycrystalline platinum electrodes has been studied by surface analysis and electrochemistry techniques. The 4-ATP monolayer was characterized by cyclic voltammetry (CV), Raman spectroscopy, reflection absorption infrared (RAIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) experiments give an idea about the packing quality of the monolayer. RAIR and Raman spectra for 4-ATP modified platinum electrodes showed the characteristic adsorption bands for neat 4-ATP indicating the adsorption of 4-ATP molecules on platinum surface. The adsorption on platinum was also evidenced by the presence of sulfur and nitrogen peaks by XPS survey spectra of the modified platinum electrodes. High resolution XPS studies and RAIR spectrum for platinum electrodes modified with 4-ATP indicate that molecules are sulfur-bonded to the platinum surface. The formation of S-Pt bond suggests that ATP adsorption gives up an amino terminated SAM. Thickness of the monolayer was evaluated via angle-resolved XPS (AR-XPS) analyses. Derivatization of 4-ATP SAM was performed using 16-Br hexadecanoic acid.

  13. Chemically Transformable Configurations of Mercaptohexadecanoic Acid Self-Assembled Monolayers Adsorbed on Au(111)

    SciTech Connect

    van Buuren, T; Bostedt, C; Nelson, A J; Terminello, L J; Vance, A L; Fadley, C S; Willey, T M

    2003-10-21

    Carboxyl terminated Self-Assembled Monolayers (SAMs) are commonly used in a variety of applications, with the assumption that the molecules form well ordered monolayers. In this work, NEXAFS verifies well ordered monolayers can be formed using acetic acid in the solvent. Disordered monolayers with unbound molecules present in the result using only ethanol. A stark reorientation occurs upon deprotonation of the endgroup by rinsing in a KOH solution. This reorientation of the endgroup is reversible with tilted over, hydrogen bound carboxyl groups while carboxylate-ion endgroups are upright. C1s photoemission shows that SAMs formed and rinsed with acetic acid in ethanol, the endgroups are protonated, while without, a large fraction of the molecules on the surface are carboxylate terminated.

  14. Hot-rolling nanowire transparent electrodes for surface roughness minimization.

    PubMed

    Hosseinzadeh Khaligh, Hadi; Goldthorpe, Irene A

    2014-01-01

    Silver nanowire transparent electrodes are a promising alternative to transparent conductive oxides. However, their surface roughness presents a problem for their integration into devices with thin layers such as organic electronic devices. In this paper, hot rollers are used to soften plastic substrates with heat and mechanically press the nanowires into the substrate surface. By doing so, the root-mean-square surface roughness is reduced to 7 nm and the maximum peak-to-valley value is 30 nm, making the electrodes suitable for typical organic devices. This simple process requires no additional materials, which results in a higher transparency, and is compatible with roll-to-roll fabrication processes. In addition, the adhesion of the nanowires to the substrate significantly increases.

  15. Long-range surface plasmons in electrode structures

    NASA Technical Reports Server (NTRS)

    Stegeman, G. I.; Burke, J. J.

    1983-01-01

    Surface polaritons guided by symmetric double metal film structures are analyzed, with particular attention given to the attenuation of the two long-range modes that occur. It is found that long-range surface plasmon polariton modes do exist for double electrode structures over a limited range of material parameters. Guided by thin metal electrodes, surface plasmon polaritons can achieve millimeter plus propagation distances in the near infrared. It is pointed out that if the slab is electrooptic, then very low voltages will be needed to manipulate the waves. The fact that long-range modes exist simultaneously with junction tunnel plasmons may be of use in providing directional radiation from light-emitting junctions or the inverse process of light to electrical energy conversion.

  16. High surface area, low weight composite nickel fiber electrodes

    NASA Technical Reports Server (NTRS)

    Johnson, Bradley A.; Ferro, Richard E.; Swain, Greg M.; Tatarchuk, Bruce J.

    1993-01-01

    The energy density and power density of light weight aerospace batteries utilizing the nickel oxide electrode are often limited by the microstructures of both the collector and the resulting active deposit in/on the collector. Heretofore, these two microstructures were intimately linked to one another by the materials used to prepare the collector grid as well as the methods and conditions used to deposit the active material. Significant weight and performance advantages were demonstrated by Britton and Reid at NASA-LeRC using FIBREX nickel mats of ca. 28-32 microns diameter. Work in our laboratory investigated the potential performance advantages offered by nickel fiber composite electrodes containing a mixture of fibers as small as 2 microns diameter (Available from Memtec America Corporation). These electrode collectors possess in excess of an order of magnitude more surface area per gram of collector than FIBREX nickel. The increase in surface area of the collector roughly translates into an order of magnitude thinner layer of active material. Performance data and advantages of these thin layer structures are presented. Attributes and limitations of their electrode microstructure to independently control void volume, pore structure of the Ni(OH)2 deposition, and resulting electrical properties are discussed.

  17. Insight on the surface polarisation for non-blocking electrodes

    NASA Astrophysics Data System (ADS)

    de Andrade, T.; Alexe-Ionescu, A. L.; Saracco, G.; Barbero, G.

    2016-03-01

    A complete phenomenological description of the electrode polarisation and of the non-blocking character of electrodes is theoretically discussed. To do this, the role of the ions on the electrical response of an electrolytic cell submitted to an external field of small amplitude is investigated. We assume that the conduction current across the electrodes is limited by energy barriers which determine the activation energy of the corresponding electrochemical reactions responsible for the processes of charge transfer between the solution containing ions and the external circuit. This assumption implies that the boundary conditions for the conduction current on the electrodes contain two terms: one proportional to the surface electric field, as in the Ohmic model, and the other proportional to the surface variation of the bulk concentration of ions, as in the Chang-Jaffe model. We deduce, in the one-mobile ion approximation, the expression for the electric impedance of the cell, in the shape of a slab, for mixed boundary conditions. Our expression contains, as particular cases, the Ohmic and Chang-Jaffe models. The equivalence between the general case considered in our analysis and previous models is discussed.

  18. Cryogenic ion trapping systems with surface-electrode traps.

    PubMed

    Antohi, P B; Schuster, D; Akselrod, G M; Labaziewicz, J; Ge, Y; Lin, Z; Bakr, W S; Chuang, I L

    2009-01-01

    We present two simple cryogenic rf ion trap systems in which cryogenic temperatures and ultra high vacuum pressures can be reached in as little as 12 h. The ion traps are operated either in a liquid helium bath cryostat or in a low vibration closed cycle cryostat. The fast turn around time and availability of buffer gas cooling made the systems ideal for testing surface-electrode ion traps. The vibration amplitude of the closed cycled cryostat was found to be below 106 nm. We evaluated the systems by loading surface-electrode ion traps with (88)Sr(+) ions using laser ablation, which is compatible with the cryogenic environment. Using Doppler cooling we observed small ion crystals in which optically resolved ions have a trapped lifetime over 2500 min.

  19. Li{sup +}-ion neutralization on metal surfaces and thin films

    SciTech Connect

    Chen Lin; Shen Jie; Jia Juanjuan; Kandasamy, Thirunavukkarasu; Bobrov, Kirill; Guillemot, Laurent; Esaulov, Vladimir A.; Fuhr, Javier D.; Martiarena, Maria Luz

    2011-11-15

    Li{sup +} ions with energies ranging from 0.3 to 2 keV are scattered from Au(110) and Pd(100) surfaces and from ultrathin Ag film grown on Au(111) in order to study electron transfer phenomena. We find that neutralization occurs quite efficiently and find an anomalous ion energy dependence of the neutral fraction for Au(110) and Pd(100) surfaces previously noted for Au(111). The dependence of the neutral fraction on the azimuthal angle of the Au(110) and Pd(100) surfaces is reported. In the case of Ag monolayer on Au(111), results are similar to the case of the Ag(111) surface. To understand the anomalous ion energy dependence, we present a theoretical study using density functional theory (DFT) and a linearized rate equation approach, which allows us to follow the Li charge state evolution for the (111) surfaces of Ag, Au, and Cu, and for the Ag-covered Au(111) surface.

  20. Electrochemical surface plasmon resonance sensor based on two-electrode configuration

    NASA Astrophysics Data System (ADS)

    Zhang, Bing; Li, Yazhuo; Dong, Wei; Wen, Yizhang; Pang, Kai; Zhan, Shuyue; Wang, Xiaoping

    2016-10-01

    To obtain detailed information about electrochemistry reactions, a two-electrode electrochemical surface plasmon resonance (EC-SPR) sensor has been proposed. We describe the theory of potential modulation for this novel sensor and determine the factors that can change the SPR resonance angle. The reference electrode in three-electrode configuration was eliminated, and comparing with several other electrode materials, activated carbon (AC) is employed as the suitable counter electrode for its potential stability. Just like three-electrode configuration, the simpler AC two-electrode system can also obtain detailed information about the electrochemical reactions.

  1. Experimental demonstration of a surface-electrode multipole ion trap

    NASA Astrophysics Data System (ADS)

    Maurice, Mark; Allen, Curtis; Green, Dylan; Farr, Andrew; Burke, Timothy; Hilleke, Russell; Clark, Robert

    2015-08-01

    We report on the design and experimental characterization of a surface-electrode multipole ion trap. Individual microscopic sugar particles are confined in the trap. The trajectories of driven particle motion are compared with a theoretical model, both to verify qualitative predictions of the model and to measure the charge-to-mass ratio of the confined particle. The generation of harmonics of the driving frequency is observed as a key signature of the nonlinear nature of the trap. We remark on possible applications of our traps, including to mass spectrometry.

  2. Energy level alignment of single-wall carbon nanotubes on metal surfaces

    NASA Astrophysics Data System (ADS)

    Clair, Sylvain; Kim, Yousoo; Kawai, Maki

    2011-06-01

    We studied the electronic configuration of single-wall carbon nanotubes adsorbed on well-defined Au(111) and Cu(111) surfaces. We found opposite behaviors for their energy-level alignment with metal: nanotubes are p-doped on Au(111) and n-doped on Cu(111). The doping level is not uniquely defined for a particular metal surface but rather exhibits a distribution depending on several uncontrolled factors such as nanotube geometry and adsorption configuration.

  3. Slow and fast capacitive process taking place at the ionic liquid/electrode interface.

    PubMed

    Roling, Bernhard; Drüschler, Marcel; Huber, Benediki

    2012-01-01

    Electrochemical impedance spectroscopy was used to characterise the interface between the ultrapure room temperature ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate and a Au(111) working electrode at electrode potentials more positive than the open circuit potential (-0.14 V vs. Pt pseudo-reference). Plots of the potential-dependent data in the complex capacitance plane reveal the existence of a fast and a slow capacitive process. In order to derive the contribution of both processes to the overall capacitance, the complex capacitance data were fitted using an empirical Cole-Cole equation. The differential capacitance of the fast process is almost constant between -0.14 V and +0.2 V (vs. Pt pseudo-reference) and decreases at more positive potentials, while the differential capacitance of the slower process exhibits a maximum at +0.2 V. This maximum leads to a maximum in the overall differential capacitance. We attribute the slow process to charge redistributions in the innermost ion layer, which require an activation energy in excess of that for ion transport in the room temperature ionic liquid. The differential capacitance maximum of the slow process at +0.2 V is most likely caused by reorientations of the 1-butyl-1l-methylpyrrolidinium cations in the innermost layer with the positively charged ring moving away from the Au(111) surface and leaving behind voids which are then occupied by anions. In a recent Monte Carlo simulation by Federov, Georgi and Kornyshev (Electrochem. Commun. 2010, 12, 296), such a process was identified as the origin of a differential capacitance maximum in the anodic regime. Our results suggest that the time scales of capacitive processes at the ionic liquid/metal interface are an important piece of information and should be considered in more detail in future experimental and theoretical studies.

  4. Increased bandwidth for dielectric spectroscopy of proteins through electrode surface preparation

    NASA Astrophysics Data System (ADS)

    Mellor, Brett L.; Cortés, Efrén Cruz; Khadka, Shiul; Mazzeo, Brian A.

    2012-01-01

    Dielectric spectroscopy measurements of liquids are often limited by electrode polarization. The influence of surface polishing and deposition of the conducting polymer polypyrrole/polystyrenesulfonate (PPy/PSS) on the polarization impedance is investigated. A quantitative description of the electrode polarization contribution to the real-valued permittivity spectrum is derived. This description explains the origin of the ω ^{-const}. (textrm {const}.>1) dependency commonly observed in permittivity measurements. Electrode surface roughness is correlated with both the magnitude and phase of the constant phase element. Generally, rougher electrodes have better performance, and an order of magnitude bandwidth improvement is achieved using PPy/PSS electrodes.

  5. Speciation of Adsorbed Phosphate at Gold Electrodes: A Combined Surface-Enhanced Infrared Absorption Spectroscopy and DFT Study.

    PubMed

    Yaguchi, Momo; Uchida, Taro; Motobayashi, Kenta; Osawa, Masatoshi

    2016-08-18

    Despite the significance of phosphate buffer solutions in (bio)electrochemistry, detailed adsorption properties of phosphate anions at metal surfaces remain poorly understood. Herein, phosphate adsorption at quasi-Au(111) surfaces prepared by a chemical deposition technique has been systematically investigated over a wide range of pH by surface-enhanced infrared absorption spectroscopy in the ATR configuration (ATR-SEIRAS). Two different pH-dependent states of adsorbed phosphate are spectroscopically detected. Together with DFT calculations, the present study reveals that pKa for adsorbed phosphate species at the interface is much lower than that for phosphate species in the bulk solution; the dominant phosphate anion, H2PO4(-) at 2 < pH < 7 or HPO4(2-) at 7 < pH < 12, undergoes deprotonation upon adsorption and transforms into the adsorbed HPO4 or PO4, respectively. This study leads to a conclusion different than earlier spectroscopic studies have reached, highlighting the capability of the ATR-SEIRAS technique at electrified metal-solution interfaces. PMID:27453430

  6. Formation of a 1,8-octanedithiol self-assembled monolayer on Au(111) prepared in a lyotropic liquid-crystalline medium.

    PubMed

    García Raya, Daniel; Madueño, Rafael; Blázquez, Manuel; Pineda, Teresa

    2010-07-20

    A characterization of the 1,8-octanedithiol (ODT) self-assembled monolayer (SAM) formed from a Triton X-100 lyotropic medium has been conducted by electrochemical techniques. It is found that an ODT layer of standing-up molecules is obtained at short modification time without removing oxygen from the medium. The electrochemical study shows that the ODT layer formed after 15 min of modification time has similar electron-transfer blocking properties to the layers formed from organic solvents at much longer modification times. On the basis of XPS data, it is demonstrated that the inability to bind gold nanoparticles (AuNPs) is due to the presence of extra ODT molecules either interdigited or on top of the layer. Treatment consisting of an acid washing step following the formation of the ODT-Au(111) SAM produces a layer that is able to attach AuNPs as demonstrated by electrochemical techniques and atomic force microscopy (AFM) images.

  7. Direct patterning of negative nanostructures on self-assembled monolayers of 16-mercaptohexadecanoic acid on Au(111) substrate via dip-pen nanolithography

    NASA Astrophysics Data System (ADS)

    Zheng, Zhikun; Yang, Menglong; Liu, Yaqing; Zhang, Bailin

    2006-11-01

    Both bare and self-assembled monolayer (SAM) protected gold substrate could be etched by allyl bromide according to atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometric (ICPMS) analysis results. With this allyl bromide ink material, negative nanopatterns could be fabricated directly by dip-pen nanolithography (DPN) on SAMs of 16-mercaptohexadecanoic acid (MHA) on Au(111) substrate. A tip-promoted etching mechanism was proposed where the gold-reactive ink could penetrate the MHA resist film through tip-induced defects resulting in local corrosive removal of the gold substrate. The fabrication mechanism was also confirmed by electrochemical characterization, energy dispersive spectroscopy (EDS) analysis and fabrication of positive nanopatterns via a used DPN tip.

  8. Molecular structure and chiral separation in {alpha}-sexithiophene ultrathin films on Au(111): Low-energy electron diffraction and scanning tunneling microscopy

    SciTech Connect

    Kiel, Mario; Duncker, Klaus; Hagendorf, Christian; Widdra, Wolf

    2007-05-15

    The adsorption of the {pi}-conjugated organic molecule {alpha}-sexithiophene which is widely used in molecular electronics has been studied on Au(111) by low-energy electron diffraction and scanning tunneling microscopy. For monolayer adsorption at room temperature, large, well-ordered domains of flat-lying molecules which arrange in molecular rows are observed. A detailed structure analysis reveals an incommensurate, line-on-line oriented monolayer with one molecule per unit cell. In contrast to the behavior in the three-dimensional bulk structure, flat-lying adsorption introduces molecular chirality: Right- and left-handed molecules separate into domains of different orientations which are mirror symmetric with respect to the [112] substrate direction. Details of the adlayer structure and the chiral self-recognition can be rationalized based on the van der Waals contour of the adsorbed molecules.

  9. Formation of a 1,8-octanedithiol self-assembled monolayer on Au(111) prepared in a lyotropic liquid-crystalline medium.

    PubMed

    García Raya, Daniel; Madueño, Rafael; Blázquez, Manuel; Pineda, Teresa

    2010-07-20

    A characterization of the 1,8-octanedithiol (ODT) self-assembled monolayer (SAM) formed from a Triton X-100 lyotropic medium has been conducted by electrochemical techniques. It is found that an ODT layer of standing-up molecules is obtained at short modification time without removing oxygen from the medium. The electrochemical study shows that the ODT layer formed after 15 min of modification time has similar electron-transfer blocking properties to the layers formed from organic solvents at much longer modification times. On the basis of XPS data, it is demonstrated that the inability to bind gold nanoparticles (AuNPs) is due to the presence of extra ODT molecules either interdigited or on top of the layer. Treatment consisting of an acid washing step following the formation of the ODT-Au(111) SAM produces a layer that is able to attach AuNPs as demonstrated by electrochemical techniques and atomic force microscopy (AFM) images. PMID:20578682

  10. Attaching Thiolated Superconductor Grains on Gold Surfaces for Nanoelectronics Applications

    NASA Astrophysics Data System (ADS)

    De Los Santos Valladares, Luis; Bustamante Dominguez, Angel; Llandro, Justin; Suzuki, Seiichi; Mitrelias, Thanos; Bellido Quispe, Richard; Barnes, Crispin H. W.; Majima, Yutaka

    2010-09-01

    We report that the high critical temperature superconductor (HTCS) LaCaBaCu3O7 in the form of nanograins can be linked to Au(111) surfaces through self assembled monolayers (SAMs) of HS-C8H16-HS [octane (di)thiol]. We show that La1113 particles (100 nm mean diameter) can be functionalized by octane (di)thiol without affecting their superconducting critical temperature (TC=80 K). X-ray photoemission spectroscopy (XPS) analysis reveals that the thiol functional heads link the superconducting grain surfaces creating sulfonates and we deduce that bonding between the S atoms and Cu(1) atoms of the La1113 structure would be formed. We suggest a design for a superconducting transistor fabricated by immobilized La1113 nanograins in between two gold electrodes which could be controlled by an external magnetic field gate.

  11. Repeatability of phasic muscle activity: performance of surface and intramuscular wire electrodes in gait analysis.

    PubMed

    Kadaba, M P; Wootten, M E; Gainey, J; Cochran, G V

    1985-01-01

    Repeatability is an important consideration for gait analysis data that are being used as an adjunct to clinical decision making. An index of repeatability may be based on a statistical criterion (variance ratio) that reflects similarity of wave forms over a number of identical cycles. The purpose of this study was to use the variance ratio to assess the repeatability of phasic muscle activity recorded with surface and bipolar intramuscular wire electrodes during gait on 10 normal subjects. Variance ratios were calculated using rectified and smoothed electromyographic data recorded simultaneously from the two types of electrodes. Three measures of repeatability (reproducibility, reliability, and constancy--defined as the cycle-to-cycle, run-to-run, and day-to-day repeatability of phasic muscle activity) were used to compare the performance of the two electrode techniques. Results show that the reproducibility and reliability were better for surface electrodes than for intramuscular wire electrodes, and constancy was good for surface electrodes and poor for intramuscular wire electrodes. Repeatability improved with increasing smoothing window lengths but was better for surface electrodes than wire electrodes, irrespective of the smoothing window. This study indicates that surface electrode data represent a more consistent measure of activity of superficial muscles, if comparisons are to be made between gait data from different test days.

  12. Restructuring of an Ir(210) electrode surface by potential cycling

    PubMed Central

    Soliman, Khaled A; Kolb, Dieter M; Jacob, Timo

    2014-01-01

    Summary This study addresses the electrochemical surface faceting and restructuring of Ir(210) single crystal electrodes. Cyclic voltammetry measurements and in situ scanning tunnelling microscopy are used to probe structural changes and variations in the electrochemical behaviour after potential cycling of Ir(210) in 0.1 M H2SO4. Faceted structures are obtained electrochemically as a function of time by cycling at a scanrate of 1 V·s−1 between −0.28 and 0.70 V vs SCE, i.e., between the onset of hydrogen evolution and the surface oxidation regime. The electrochemical behaviour in sulfuric acid solution is compared with that of thermally faceted Ir(210), which shows a sharp characteristic voltammetric peak for (311) facets. Structures similar to thermally-induced faceted Ir(210) are obtained electrochemically, which typically correspond to polyoriented facets at nano-pyramids. These structures grow anisotropically in a preferred direction and reach a height of about 5 nm after 4 h of cycling. The structural changes are reflected in variations of the electrocatalytic activity towards carbon monoxide adlayer oxidation. PMID:25247118

  13. Diffusional protection of electrode surfaces using regular arrays of immobilised droplets: overcoming interferences in electroanalysis.

    PubMed

    Simm, Andrew O; Ordeig, Olga; Del Campo, Javier; Muñoz, Francesc Xavier; Compton, Richard G

    2006-09-01

    Regular arrays of ca. micron sized droplets on a gold electrode surface can block diffusion to the electrode surface of one metal ion (which binds with the material in the droplet) whilst having no significant effect on another (which does not), so allowing interference effects in electroanalysis to be eliminated.

  14. How voltage drops are manifested by lithium ion configurations at interfaces and in thin films on battery electrodes

    DOE PAGES

    Leung, Kevin; Leenheer, Andrew Jay

    2015-04-09

    Battery electrode surfaces are generally coated with electronically insulating solid films of thickness 1-50 nm. Both electrons and Li+ can move at the electrode–surface film interface in response to the voltage, which adds complexity to the “electric double layer” (EDL). We also apply Density Functional Theory (DFT) to investigate how the applied voltage is manifested as changes in the EDL at atomic length scales, including charge separation and interfacial dipole moments. Illustrating examples include Li3PO4, Li2CO3, and LixMn2O4 thin films on Au(111) surfaces under ultrahigh vacuum conditions. Adsorbed organic solvent molecules can strongly reduce voltages predicted in vacuum. We proposemore » that manipulating surface dipoles, seldom discussed in battery studies, may be a viable strategy to improve electrode passivation. We also distinguish the computed potential governing electrons, which is the actual or instantaneous voltage, and the “lithium cohesive energy”-based voltage governing Li content widely reported in DFT calculations, which is a slower-responding self-consistency criterion at interfaces. Furthermore, this distinction is critical for a comprehensive description of electrochemical activities on electrode surfaces, including Li+ insertion dynamics, parasitic electrolyte decomposition, and electrodeposition at overpotentials.« less

  15. How voltage drops are manifested by lithium ion configurations at interfaces and in thin films on battery electrodes

    SciTech Connect

    Leung, Kevin; Leenheer, Andrew Jay

    2015-04-09

    Battery electrode surfaces are generally coated with electronically insulating solid films of thickness 1-50 nm. Both electrons and Li+ can move at the electrode–surface film interface in response to the voltage, which adds complexity to the “electric double layer” (EDL). We also apply Density Functional Theory (DFT) to investigate how the applied voltage is manifested as changes in the EDL at atomic length scales, including charge separation and interfacial dipole moments. Illustrating examples include Li3PO4, Li2CO3, and LixMn2O4 thin films on Au(111) surfaces under ultrahigh vacuum conditions. Adsorbed organic solvent molecules can strongly reduce voltages predicted in vacuum. We propose that manipulating surface dipoles, seldom discussed in battery studies, may be a viable strategy to improve electrode passivation. We also distinguish the computed potential governing electrons, which is the actual or instantaneous voltage, and the “lithium cohesive energy”-based voltage governing Li content widely reported in DFT calculations, which is a slower-responding self-consistency criterion at interfaces. Furthermore, this distinction is critical for a comprehensive description of electrochemical activities on electrode surfaces, including Li+ insertion dynamics, parasitic electrolyte decomposition, and electrodeposition at overpotentials.

  16. Surface analysis of supercapacitor electrodes after long-lasting constant current tests

    NASA Astrophysics Data System (ADS)

    Jänes, Alar; Eskusson, Jaanus; Lust, Enn

    2013-12-01

    FIB-SEM, XPS, TOF-SIMS and electrochemical methods have been used for the characterisation of physical properties and chemical composition of microporous carbide derived carbon electrodes, prepared from TiC at 950 °C (noted as TiC-CDC) after 40000 charge/discharge cycles. Changes in surface chemical composition of TiC-CDC electrodes, includes partial contamination with reaction intermediates (F2, CHO-, CN-, organic radicals), and Al current collectors, like partial dissolution of Al from positively charged electrode and deposition of Al onto the negatively charged TiC-CDC electrode surface, have been analysed.

  17. Platinum electrode modification: Unique surface carbonization approach to improve performance and sensitivity.

    PubMed

    Lee, Hwi Yong; Barber, Cedrick; Minerick, Adrienne R

    2015-08-01

    Many microfluidic devices, also known as lab-on-a-chip devices, employ electrochemical detection methods using microelectrodes. Miniaturizing electrodes inevitably reduces electrode sensitivity and decreases the S/N, which limits applications within microfluidic devices. However, microelectrode surface modification can increase the surface area and sensitivity. In the present work, we report substantial improvement in platinum electrode performance and sensitivity by coating with carbon from red blood cells. The larger goal of this work was to measure DC electrical resistances of red blood cell suspensions in a microchannel for hematocrit determination. It was observed that as current responses of red blood cell suspensions were measured, the platinum electrode performance (reproducibility and S/N) improved with time. The platinum electrode electrocatalytic activity for red blood cell current measurements improved by 140%. Systematic experimentation revealed that red blood cells adsorb and carbonize the platinum electrode surfaces. The electrode surfaces before and after performance improvements were analyzed by field emission scanning electron microscopy, energy dispersive spectrometry, and Raman spectrometry. The formed carbon layers on the electrode surfaces were found to be proteomic and increased surface area with a porous three-dimensional structure, thus improving performance and stabilizing currents.

  18. Transition voltages of vacuum-spaced and molecular junctions with Ag and Pt electrodes

    SciTech Connect

    Wu, Kunlin; Bai, Meilin; Hou, Shimin; Sanvito, Stefano

    2014-07-07

    The transition voltage of vacuum-spaced and molecular junctions constructed with Ag and Pt electrodes is investigated by non-equilibrium Green's function formalism combined with density functional theory. Our calculations show that, similarly to the case of Au-vacuum-Au previously studied, the transition voltages of Ag and Pt metal-vacuum-metal junctions with atomic protrusions on the electrode surface are determined by the local density of states of the p-type atomic orbitals of the protrusion. Since the energy position of the Pt 6p atomic orbitals is higher than that of the 5p/6p of Ag and Au, the transition voltage of Pt-vacuum-Pt junctions is larger than that of both Ag-vacuum-Ag and Au-vacuum-Au junctions. When one moves to analyzing asymmetric molecular junctions constructed with biphenyl thiol as central molecule, then the transition voltage is found to depend on the specific bonding site for the sulfur atom in the thiol group. In particular agreement with experiments, where the largest transition voltage is found for Ag and the smallest for Pt, is obtained when one assumes S binding at the hollow-bridge site on the Ag/Au(111) surface and at the adatom site on the Pt(111) one. This demonstrates the critical role played by the linker-electrode binding geometry in determining the transition voltage of devices made of conjugated thiol molecules.

  19. Surface-enhanced Raman scattering of single-walled carbon nanotubes on modified silver electrode

    NASA Astrophysics Data System (ADS)

    Hou, Xiaomiao; Fang, Yan

    2008-04-01

    A roughed silver electrode modified with gold/silver nanoparticles is used as a substrate, on which high quality SERS of SWCNTs are obtained, indicating that the modified silver electrode is a high-quality SERS-active substrate for SWCNTs. Some new bands that indicate the structure of SWCNTs were obtained. The gold/silver nanoparticles modified on the roughed silver electrode surface can not only make sure the strong adsorption of SWCNTs in this system but also play an important role in magnifying the surface local electric field near the silver electrode surface through resonant surface plasmon excitation. From the rich information on the modified silver electrode obtained from the SERS and the potential dependent SERS, we may deduce the probable SERS mechanism in the process. The theory and experiment results indicate that it is can be used as a new technique for monitoring synthesis quality of SWCNTs. The probable reasons are given.

  20. Ethanol oxidation on Pt single-crystal electrodes: surface-structure effects in alkaline medium.

    PubMed

    Busó-Rogero, Carlos; Herrero, Enrique; Feliu, Juan M

    2014-07-21

    Ethanol oxidation in 0.1 M NaOH on single-crystal electrodes has been studied using electrochemical and FTIR techniques. The results show that the activity order is the opposite of that found in acidic solutions. The Pt(111) electrode displays the highest currents and also the highest onset potential of all the electrodes. The onset potential for the oxidation of ethanol is linked to the adsorption of OH on the electrode surface. However, small (or even negligible) amounts of CO(ads) and carbonate are detected by FTIR, which implies that cleavage of the C-C bond is not favored in this medium. The activity of the electrodes diminishes quickly upon cycling. The diminution of the activity is proportional to the measured currents and is linked to the formation and polymerization of acetaldehyde, which adsorbs onto the electrode surface and prevents further oxidation. PMID:24782218

  1. High Conductivity Water Treatment Using Water Surface Discharge with Nonmetallic Electrodes

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoping; Zhang, Xingwang; Lei, Lecheng

    2013-06-01

    Although electrohydraulic discharge is effective for wastewater treatment, its application is restricted by water conductivity and limited to the treatment of low conductivity water. For high conductivity water treatment, water-surface discharge is the preferred choice. However, the metallic electrodes are easily corroded because of the high temperature and strong oxidative environment caused by gas phase discharge and the electrochemical reaction in water. As a result, the efficiency of the water treatment might be affected and the service life of the reactor might be shortened. In order to avoid the corrosion problem, nonmetallic electrode water-surface discharge is introduced into high conductivity water treatment in the present study. Carbon-felt and water were used as the high voltage electrode and ground electrode, respectively. A comparison of the electrical and chemical characteristics showed that nonmetallic electrode discharge maintained the discharge characteristics and enhanced the energy efficiency, and furthermore, the corrosion of metal electrodes was avoided.

  2. Further observations of the surface enhanced Raman spectrum of water on silver and copper electrodes

    NASA Astrophysics Data System (ADS)

    Pettinger, B.; Philpott, Michael R.; Gordon, Joseph G.

    1981-04-01

    Two methods useful for detecting surface enhanced Raman (SER) spectra of water on Ag and Cu electrodes are described. The first method uses potential difference spectroscopy to record the SER spectrum of water on a Cu electrode. The second method obtains a SER spectrum of water on an emersed silver electrode. Emersion is a promising technique for reducing the interference from the Raman scattering of bulk water.

  3. In situ plasma removal of surface contaminants from ion trap electrodes

    SciTech Connect

    Haltli, Raymond A.

    2015-05-01

    In this thesis, the construction and implementation of an in situ plasma discharge designed to remove surface contaminants from electrodes in an ion trapping experimental system is presented with results. In recent years, many advances have been made in using ion traps for quantum information processing. All of the criteria defined by DiVincenzo for using ion traps for implementing a quantum computer have been individually demonstrated, and in particular surface traps provide a scalable platform for ions. In order to be used for quantum algorithms, trapped ions need to be cooled to their motional (quantum mechanical) ground state. One of the hurdles in integrating surface ion traps for a quantum computer is minimizing electric field noise, which causes the ion to heat out of its motional ground state and which increases with smaller ion-to-electrode distances realized with surface traps. Surface contamination of trap electrodes is speculated to be the primary source of electric field noise. The main goal achieved by this work was to implement an in situ surface cleaning solution for surface electrode ion traps, which would not modify the ion trap electrode surface metal. Care was taken in applying the RF power in order to localize a plasma near the trap electrodes. A method for characterizing the energy of the plasma ions arriving at the ion trap surface is presented and results for plasma ion energies are shown. Finally, a method for quantifying the effectiveness of plasma cleaning of trap electrodes, using the surface analysis technique of X-ray photoelectron spectroscopy for measuring the amount and kind of surface contaminants, is described. A significant advantage of the trap electrode surface cleaning method presented here is the minimal changes necessary for implementation on a working ion trap experimental system.

  4. Shape correction of optical surfaces using plasma chemical vaporization machining with a hemispherical tip electrode.

    PubMed

    Takino, Hideo; Yamamura, Kazuya; Sano, Yasuhisa; Mori, Yuzo

    2012-01-20

    We propose a plasma chemical vaporization machining device with a hemispherical tip electrode for optical fabrication. Radio-frequency plasma is generated close to the electrode under atmospheric conditions, and a workpiece is scanned relative to the stationary electrode under three-axis motion control to remove target areas on a workpiece surface. Experimental results demonstrate that surface removal progresses although process gas is not forcibly supplied to the plasma. The correction of shape errors on conventionally polished spheres is performed. As a result, highly accurate smooth surfaces with the desired rms shape accuracy of 3 nm are successfully obtained, which confirms that the device is effective for the fabrication of optics.

  5. Electrode-electrolyte impedance due to polarization: influence of surface roughness

    NASA Astrophysics Data System (ADS)

    Mazzeo, Brian; Cruz Cortes, Efren; Mellor, Brett

    2011-10-01

    Many new measurement paradigms make use of microelectrodes for interrogating liquids and biological tissues. Double-layer formation at the electrode-electrolyte interface contributes to the measured impedance of the electrode surface in series with the substance that is being measured. An empirical constant phase element is often used to model the impedance of the interface. Engineering the surface thus provides a path to reduce the influence of electrode polarization in liquid measurements. Here, the surface roughness is used to modify the interfacial impedance, greatly increasing the available bandwidth for dielectric spectroscopy of protein solutions.

  6. Specific and efficient adsorption of phosphorothioated DNA on Au-based surfaces and electrodes

    NASA Astrophysics Data System (ADS)

    Ghabboun, Jamal; Sowwan, Mukhles; Cohen, Hezy; Molotsky, Tatiana; Borovok, Natalia; Dwir, Benjamin; Kapon, Eli; Kotlyar, Alexander; Porath, Danny

    2007-10-01

    Efficient attachment of DNA to metal surfaces or electrodes is essential for charge-transport measurements, scanning tunneling microscopy, and for devices and sensors. To optimize DNA deposition on Au-based surfaces and electrodes, we synthesized DNA with phosphorothioate (PT) groups attached to the G strand of poly(deoxyguanine)-poly(deoxycytosine) [poly(dG)-poly(dC)]. This procedure strongly improves the DNA anchoring to Au-based surfaces by sulfur-gold interaction. Much higher molecular surface density on Au substrates was observed for PT poly(dG)-poly(dC) compared to "bare" molecules. Deposition of PT poly(dG)-poly(dC) on Au-based electrodes, followed by thorough washing, showed that they specifically attach to the electrodes and are not spread on the surrounding SiO2 surface.

  7. Effects of electrode surface roughness on motional heating of trapped ions

    NASA Astrophysics Data System (ADS)

    Lin, Kuan-Yu; Low, Guang Hao; Chuang, Isaac L.

    2016-07-01

    Electric-field noise is a major source of motional heating in trapped-ion quantum computation. While the influence of trap-electrode geometries on electric-field noise has been studied in patch potential and surface adsorbate models, only smooth surfaces are accounted for by current theory. The effects of roughness, a ubiquitous feature of surface electrodes, are poorly understood. We investigate its impact on electric-field noise by deriving a rough-surface Green's function and evaluating its effects on adsorbate-surface binding energies. At cryogenic temperatures, heating-rate contributions from adsorbates are predicted to exhibit an exponential sensitivity to local surface curvature, leading to either a large net enhancement or suppression over smooth surfaces. For typical experimental parameters, orders-of-magnitude variations in total heating rates can occur depending on the spatial distribution of adsorbates. Through careful engineering of electrode surface profiles, our results suggests that heating rates can be tuned over orders of magnitudes.

  8. Electrochemical oxidation of hydrazine and its derivatives on the surface of metal electrodes in alkaline media

    NASA Astrophysics Data System (ADS)

    Asazawa, Koichiro; Yamada, Koji; Tanaka, Hirohisa; Taniguchi, Masatoshi; Oguro, Keisuke

    Electrochemical oxidation of hydrazine and its derivatives on the surface of various metal electrodes in alkaline media was investigated. A comparison of various polycrystalline metal electrodes (Ni, Co, Fe, Cu, Ag, Au, and Pt) showed that Co and Ni electrodes have a lower onset potential for hydrazine oxidation than the Pt electrode. The onset oxidation potential of APA (aminopolyacrylamide), a hydrazine derivative (-0.127 V vs. reversible hydrogen electrode, RHE), was similar to that of hydrazine hydrate (-0.178 V vs. RHE) in the case of the Co electrode. APA oxidation was possible because of hydrazine desorption that was caused by APA hydrolysis. The hydrolysis reaction was brought about by a heat treatment. This result suggests that the hydrazine hydrolysis reaction of hydrazine derivatives makes it possible to store hydrazine hydrate safely.

  9. Investigation of the deposition and thermal behavior of striped phases of unsymmetric disulfide self-assembled monolayers on Au(111): The case of 11-hydroxyundecyl decyl disulfide

    SciTech Connect

    Albayrak, Erol; Karabuga, Semistan; Bracco, Gianangelo; Danışman, M. Fatih

    2015-01-07

    Self-assembled monolayers (SAMs) of unsymmetric disulfides on Au(111) are used to form mixed SAMs that can be utilized in many applications. Here, we have studied 11-hydroxyundecyl decyl disulfide (CH{sub 3}–(CH{sub 2}){sub 9}–S–S–(CH{sub 2}){sub 11}–OH, HDD) SAMs produced by supersonic molecular beam deposition and characterized by He diffraction. The film growth was monitored at different temperatures up to a coverage which corresponds to a full lying down phase and the diffraction analysis shows that below 250 K the phase is different from the phase measured above 300 K. During the annealing of the film, two phase transitions were observed, at 250 K and 350 K. The overall data suggest that the former is related to an irreversible phase separation of HDD above 250 K to decanethiolate (–S–(CH{sub 2}){sub 9}–CH{sub 3}, DTT) and hydroxyundecylthiolate (–S–(CH{sub 2}){sub 11}–OH, MUDT), while the latter to a reversible melting of the film. Above 450 K, the specular intensity shows an increase related to film desorption and different chemisorbed states were observed with energies in the same range as observed for decanethiol (H–S–(CH{sub 2}){sub 9}–CH{sub 3}, DT) and mercaptoundecanol (H–S–(CH{sub 2}){sub 11}–OH, MUD) SAMs.

  10. Simulating Supercapacitors: Can We Model Electrodes As Constant Charge Surfaces?

    PubMed

    Merlet, Céline; Péan, Clarisse; Rotenberg, Benjamin; Madden, Paul A; Simon, Patrice; Salanne, Mathieu

    2013-01-17

    Supercapacitors based on an ionic liquid electrolyte and graphite or nanoporous carbon electrodes are simulated using molecular dynamics. We compare a simplified electrode model in which a constant, uniform charge is assigned to each carbon atom with a realistic model in which a constant potential is applied between the electrodes (the carbon charges are allowed to fluctuate). We show that the simulations performed with the simplified model do not provide a correct description of the properties of the system. First, the structure of the adsorbed electrolyte is partly modified. Second, dramatic differences are observed for the dynamics of the system during transient regimes. In particular, upon application of a constant applied potential difference, the increase in the temperature, due to the Joule effect, associated with the creation of an electric current across the cell follows Ohm's law, while unphysically high temperatures are rapidly observed when constant charges are assigned to each carbon atom. PMID:26283432

  11. Simulating Supercapacitors: Can We Model Electrodes As Constant Charge Surfaces?

    PubMed

    Merlet, Céline; Péan, Clarisse; Rotenberg, Benjamin; Madden, Paul A; Simon, Patrice; Salanne, Mathieu

    2013-01-17

    Supercapacitors based on an ionic liquid electrolyte and graphite or nanoporous carbon electrodes are simulated using molecular dynamics. We compare a simplified electrode model in which a constant, uniform charge is assigned to each carbon atom with a realistic model in which a constant potential is applied between the electrodes (the carbon charges are allowed to fluctuate). We show that the simulations performed with the simplified model do not provide a correct description of the properties of the system. First, the structure of the adsorbed electrolyte is partly modified. Second, dramatic differences are observed for the dynamics of the system during transient regimes. In particular, upon application of a constant applied potential difference, the increase in the temperature, due to the Joule effect, associated with the creation of an electric current across the cell follows Ohm's law, while unphysically high temperatures are rapidly observed when constant charges are assigned to each carbon atom.

  12. Nature of the Surface-Exposed Cytochrome-Electrode Interactions in Electroactive Biofilms of Desulfuromonas acetoxidans.

    PubMed

    Alves, A; Ly, H K; Hildebrandt, P; Louro, R O; Millo, D

    2015-06-25

    Metal-respiring bacteria are microorganisms capable of oxidizing organic pollutants present in wastewater and transferring the liberated electrons to an electrode. This ability has led to their application as catalysts in bioelectrochemical systems (BESs), a sustainable technology coupling bioremediation to electricity production. Crucial for the functioning of these BESs is a complex protein architecture consisting of several surface-exposed multiheme proteins, called outer membrane cytochromes, wiring the cell metabolism to the electrode. Although the role of these proteins has been increasingly understood, little is known about the protein-electrode interactions and their impact on the performance of BESs. In this study, we used surface-enhanced resonance Raman spectroscopy in combination with electrochemical techniques to unravel the nature of the protein-electrode interaction for the outer membrane cytochrome OmcB from Desulfuromonas acetoxidans (Dace). Comparing the spectroelectrochemical properties of OmcB bound directly to the electrode surface with those of the same protein embedded inside an electroactive biofilm, we have shown that the surface-exposed cytochromes of Dace biofilms are in direct contact with the electrode surface. Even if direct binding causes protein denaturation, the biofilm possesses the ability to minimize the extent of the damage maximizing the amount of cells in direct electrical communication with the electrode.

  13. Silver nanowire/polyaniline composite transparent electrode with improved surface properties

    SciTech Connect

    Kumar, A.B.V. Kiran; Jiang, Jianwei; Bae, Chang Wan; Seo, Dong Min; Piao, Longhai Kim, Sang-Ho

    2014-09-15

    Highlights: • AgNWs/PANI transparent electrode was prepared by layer-by-layer coating method. • The surface roughness of the electrode reached to 6.5 nm (root mean square). • The electrode had reasonable sheet resistance (25 Ω/□) and transmittance (83.5%). - Abstract: Silver nanowires (AgNWs) are as potential candidates to replace indium tin oxide (ITO) in transparent electrodes because of their preferred conducting and optical properties. However, their rough surface properties are not favorable for the fabrication of optoelectronic devices, such as displays and thin-film solar cells. In the present investigation, AgNWs/polyaniline composite transparent electrodes with better surface properties were successfully prepared. AgNWs were incorporated into polyaniline:polystyrene sulfonate (PANI:PSS) by layer-by-layer coating and mechanical pressing. PANI:PSS decreased the surface roughness of the AgNWs electrode by filling the gap of the random AgNWs network. The transparent composite electrode had decreased surface roughness (root mean square 6.5 nm) with reasonable sheet resistance (25 Ω/□) and transmittance (83.5%)

  14. in situ plasma removal of surface contaminants from ion trap electrodes

    SciTech Connect

    Haltli, Raymond A.

    2015-04-01

    This research resulted in a construction and implementation of an in situ plasma discharge to remove surface contaminants from electrodes in an ion trapping experimental system is presented with results.

  15. Method of forming macro-structured high surface area transparent conductive oxide electrodes

    DOEpatents

    Forman, Arnold J.; Chen, Zhebo; Jaramillo, Thomas F.

    2016-01-05

    A method of forming a high surface area transparent conducting electrode is provided that includes depositing a transparent conducting thin film on a conductive substrate, where the transparent conducting thin film includes transparent conductive particles and a solution-based transparent conducting adhesive layer which serves to coat and bind together the transparent conducting particles, and heat treating the transparent conducting adhesion layer on the conductive substrate, where an increased surface area transparent conducting electrode is formed.

  16. Shaping of steel mold surface of lens array by electrical discharge machining with single rod electrode.

    PubMed

    Takino, Hideo; Hosaka, Takahiro

    2014-11-20

    We propose a method for fabricating a lens array mold by electrical discharge machining (EDM). In this method, the tips of rods are machined individually to form a specific surface, and then a number of the machined rods are arranged to construct an electrode for EDM. The repetition of the EDM process using the electrode enables a number of lens elements to be produced on the mold surface. The effectiveness of our proposed method is demonstrated by shaping a lens array mold made of stainless steel with 16 spherical elements, in which the EDM process with a single rod electrode is repeatedly conducted.

  17. Electrochemical assembling of methionine-gold nanoparticles and catalysis on the surface of glassy carbon electrode

    NASA Astrophysics Data System (ADS)

    Song, Y. Z.; Wang, J. H.; Zhang, X. M.; Cao, W.; Ge, A.; Zhou, L.

    2014-12-01

    In this paper cyclic voltammetry was used for the synthesis of linear array spherical gold nanoparticles on the surface of glassy carbon electrode using methionine as a stable reagent. The methionine-gold nanoparticles on the surface of glassy electrode were obtained. The methionine-gold nanoparticles were characterized by cyclic voltammetry, scanning electron microscopy, energy dispersive spectrometry and powder X-ray diffraction. Electrochemical behavior of methionine at methionine-gold nanoparticle modified electrode was investigated. It was demonstrated that the methionine-gold nanoparticles can catalyze electrochemical transformations of methionine.

  18. Insulator and electrode mass erosion and surface voltage holdoff recovery for transient, high current surface discharges

    NASA Astrophysics Data System (ADS)

    Engel, T. G.; Dickens, J. C.; Kristiansen, M.

    1993-01-01

    Several polymeric insulator materials commonly used as sidewall insulators in EM accelerators are subjected to repetitive, high current transient surface discharges. The insulator materials tested include the thermosetting polymers G-9, G-10, and G-11 (i.e., fiberglass reinforced melamine and epoxy) and the thermoplastic polymers Lexan (i.e, polycarbonate) and Delrin (i.e., polyacetyl). Empirical scaling relationships are given that relate the total amount of insulator and electrode (i.e., molybdenum) mass erosion versus the total amount of arc energy transferred. Scaling relationships are also given that relate the 'lifetime' of the given polymer as a function of the initial discharge current. The 'lifetime' of an insulator material is defined as the number of discharges required to reduce the initial surface holdoff voltage to its half-power level for three consecutive discharges, and is a useful parameter when specifying insulator materials to be used in high power switching devices.

  19. A motion artifact generation and assessment system for the rapid testing of surface biopotential electrodes.

    PubMed

    Cömert, Alper; Hyttinen, Jari

    2015-01-01

    Dry electrodes can reduce cost while increasing the usability and comfort of wearable monitoring systems. They are, however, susceptible to motion artifacts. The present electrode testing methods lack reliability and do not separate the factors that affect the motion artifact. In this paper, we introduce a first generation motion artifact generation and assessment system that generates the speed, amplitude, and pattern-wise programmable movement of the electrode. The system simultaneously measures electrode-skin impedance, the motion artifact, and one channel of an electrocardiogram that contains the motion artifact and monitors the mounting force applied to the electrode. We demonstrate the system by comparing the applied movement and the measured signals for electrode movements up to 6 mm and movement frequencies from 0.4 Hz to 4 Hz. Results show that the impedance change and surface potential are visually clearly related to the applied motion, with average correlations of 0.89 and 0.64, respectively. The applied force, electrode location, and electrode structure all affect the motion artifact. The setup enables the motion of the electrode to be accurately controlled. The system can be used as a precursor to the testing of integrated systems because it enables thorough, repeatable, and robust motion artifact studies. The system allows a deeper insight into motion artifacts and the interplay of the various factors that affect them.

  20. Mechanical Behavior of Free-Standing Fuel Cell Electrodes on Water Surface.

    PubMed

    Kim, Sanwi; Kim, Jae-Han; Oh, Jong-Gil; Jang, Kyung-Lim; Jeong, Byeong-Heon; Hong, Bo Ki; Kim, Taek-Soo

    2016-06-22

    Fundamental understanding of the mechanical behavior of polymer electrolyte fuel cell electrodes as free-standing materials is essential to develop mechanically robust fuel cells. However, this has been a significant challenge due to critical difficulties, such as separating the pristine electrode from the substrate without damage and precisely measuring the mechanical properties of the very fragile and thin electrodes. We report the mechanical behavior of free-standing fuel cell electrodes on the water surface through adopting an innovative ice-assisted separation method to separate the electrode from decal transfer film. It is found that doubling the ionomer content in electrodes increases not only the tensile stress at the break and the Young's modulus (E) of the electrodes by approximately 2.1-3.5 and 1.7-2.4 times, respectively, but also the elongation at the break by approximately 1.5-1.7 times, which indicates that stronger, stiffer, and tougher electrodes are attained with increasing ionomer content, which have been of significant interest in materials research fields. The scaling law relationship between Young's modulus and density (ρ) has been unveiled as E ∼ ρ(1.6), and it is compared with other materials. These findings can be used to develop mechanically robust electrodes for fuel cell applications.

  1. Mechanical Behavior of Free-Standing Fuel Cell Electrodes on Water Surface.

    PubMed

    Kim, Sanwi; Kim, Jae-Han; Oh, Jong-Gil; Jang, Kyung-Lim; Jeong, Byeong-Heon; Hong, Bo Ki; Kim, Taek-Soo

    2016-06-22

    Fundamental understanding of the mechanical behavior of polymer electrolyte fuel cell electrodes as free-standing materials is essential to develop mechanically robust fuel cells. However, this has been a significant challenge due to critical difficulties, such as separating the pristine electrode from the substrate without damage and precisely measuring the mechanical properties of the very fragile and thin electrodes. We report the mechanical behavior of free-standing fuel cell electrodes on the water surface through adopting an innovative ice-assisted separation method to separate the electrode from decal transfer film. It is found that doubling the ionomer content in electrodes increases not only the tensile stress at the break and the Young's modulus (E) of the electrodes by approximately 2.1-3.5 and 1.7-2.4 times, respectively, but also the elongation at the break by approximately 1.5-1.7 times, which indicates that stronger, stiffer, and tougher electrodes are attained with increasing ionomer content, which have been of significant interest in materials research fields. The scaling law relationship between Young's modulus and density (ρ) has been unveiled as E ∼ ρ(1.6), and it is compared with other materials. These findings can be used to develop mechanically robust electrodes for fuel cell applications. PMID:27183314

  2. Intracardiac electrogram parameters, electrode surface area and pacer input impedance: their correlations.

    PubMed

    Antonioli, E G; Baggioni, F G; Grassi, G

    1980-01-01

    Small surface area electrodes are accused of sensing defects which were related to alterations that they induce in the endocardiac electrograms. Since several factors affect the cardiac signal coming from electrode to sensing circuit, i.e. electrode surface area, electrode-tissue interface, pacemaker input impedance and sensing amplifier pass-band, Authors present their studies performed on 252 implanted electrodes of various type. Study was carried out by connecting in parallel to the recorder a variable resistor in order to simulate different pacer input impedances. The results showed a significant reduction in RS amplitude when recorder was paralleled with resistor values lower than 40 K. Slew rates showed a similar behaviours since RS steep tract did not change his duration with load, while total QRS duration is reduced. High speed analysis has shown that the RS segment is not linear in about 40% of cases: the main tract is used for calculations. The most significant attenuations and distortions of endocardial electrogram were observed with smallest electrodes and lowest resistances parallel connected: in these cases the sensing impedance at the electrode-tissue interface appears to be between 3 to 5 K ohms. The results suggest that the most of the alledged sensing faults experienced in the past were probably due to small tip electrodes connected to low input impedance generators or to impending failure situations. The AA. conclude that the main question does not concerne a true electrode inefficiency but a wrongly chosen pacemaker-electrode combination, i.e. small tip electrode connected with old generator models. To avoid the evaluation error, it would be instrumental that the pacemaker manufacturers would specify input characteristics of their generators. So, the implanting clinician becomes able to exactly evaluate the true signal arriving to the sensing circuit by connecting in parallel with the recorder input a resistor whose value approximates the input

  3. Alteration of Surface EMG amplitude levels of five major trunk muscles by defined electrode location displacement.

    PubMed

    Huebner, Agnes; Faenger, Bernd; Schenk, Philipp; Scholle, Hans-Christoph; Anders, Christoph

    2015-04-01

    Exact electrode positioning is vital for obtaining reliable results in Surface EMG. This study aimed at systematically assessing the influence of defined electrode shifts on measured Surface EMG amplitudes of trunk muscles in a group of 15 middle aged healthy male subjects. The following leftsided muscles were investigated: rectus abdominis muscle, internal and external oblique abdominal muscles, lumbar multifidus muscle, and longissimus muscle. In addition to the recommended electrode positions, extra electrodes were placed parallel to these and along muscle fiber direction. Measurements were performed under isometric conditions in upright body position. Gradually changing, but defined loads were applied considering subject's upper body weight. For the abdominal muscles amplitude differences varied considerably depending on load level, magnitude, and direction. For both back muscles amplitudes dropped consistently but rather little for parallel electrode displacements. However, for the longissimus muscle a caudal electrode shift resulted in an amplitude increase of similar extent and independent from load level. Influence of electrode position variations can be proven for all trunk muscles but are more evident in abdominal than back muscles. Those muscle-specific effects confirm the necessity for an exact definition of electrode positioning to allow comparisons between individual subjects, groups of subjects, and studies.

  4. Automated scanning probe lithography with n-alkanethiol self assembled monolayers on Au(111): Application for teaching undergraduate laboratories

    PubMed Central

    Brown, Treva T.; LeJeune, Zorabel M.; Liu, Kai; Hardin, Sean; Li, Jie-Ren; Rupnik, Kresimir; Garno, Jayne C.

    2010-01-01

    Controllers for scanning probe instruments can be programmed for automated lithography to generate desired surface arrangements of nanopatterns of organic thin films, such as n-alkanethiol self-assembled monolayers (SAMs). In this report, atomic force microscopy (AFM) methods of lithography known as nanoshaving and nanografting are used to write nanopatterns within organic thin films. Commercial instruments provide software to control the length, direction, speed, and applied force of the scanning motion of the tip. For nanoshaving, higher forces are applied to an AFM tip to selectively remove regions of the matrix monolayer, exposing bare areas of the gold substrate. Nanografting is accomplished by force-induced displacement of molecules of a matrix SAM, followed immediately by the surface self-assembly of n-alkanethiol molecules from solution. Advancements in AFM automation enable rapid protocols for nanolithography, which can be accomplished within the tight time restraints of undergraduate laboratories. Example experiments with scanning probe lithography (SPL) will be described in this report that were accomplished by undergraduate students during laboratory course activities and research internships in the chemistry department of Louisiana State University. Students were introduced to principles of surface analysis and gained “hands-on” experience with nanoscale chemistry. PMID:21483651

  5. Surface and interface engineering of electrode materials for lithium-ion batteries.

    PubMed

    Wang, Kai-Xue; Li, Xin-Hao; Chen, Jie-Sheng

    2015-01-21

    Lithium-ion batteries are regarded as promising energy storage devices for next-generation electric and hybrid electric vehicles. In order to meet the demands of electric vehicles, considerable efforts have been devoted to the development of advanced electrode materials for lithium-ion batteries with high energy and power densities. Although significant progress has been recently made in the development of novel electrode materials, some critical issues comprising low electronic conductivity, low ionic diffusion efficiency, and large structural variation have to be addressed before the practical application of these materials. Surface and interface engineering is essential to improve the electrochemical performance of electrode materials for lithium-ion batteries. This article reviews the recent progress in surface and interface engineering of electrode materials including the increase in contact interface by decreasing the particle size or introducing porous or hierarchical structures and surface modification or functionalization by metal nanoparticles, metal oxides, carbon materials, polymers, and other ionic and electronic conductive species.

  6. Kilohertz organic complementary inverters driven by surface-grafting conducting polypyrrole electrodes

    NASA Astrophysics Data System (ADS)

    Zhang, Xi; Zhang, Suna; Li, Liqiang; Chen, Xiaosong; Xu, Zeyang; Wu, Kunjie; Li, Hongwei; Meng, Yancheng; Wang, Wenchong; Hu, Wenping; Chi, Lifeng

    2016-09-01

    Surface-grafting conducting polymer has advantage to circumvent the difficulty in patterning as well as the weak interface adhesion on substrate of the conventional conducting polymer, which would be desirable for its application as electrodes in electronic devices. In this work, the patterned surface-grafting polypyrrole (PPY) is used as electrode, which shows merits such as strong interface adhesion, robustness against solvent treatment, easy scaling-up, and good conductivity. Remarkably, the surface-grafting PPY electrodes can efficiently drive both p-type and n-type organic field-effect transistors. By combining p-/n-type transistors, organic complementary inverters are constructed with PPY electrodes, which exhibit low operational voltage (<8 V), high gain (6-17), and low power dissipation (several tens of nW). The switching voltage is approximately 0.5Vdd with a high noise margin (>70% of 0.5Vdd). Dynamic switching measurements indicate that the inverter has an operational frequency of about 3.3 kHz. This is the first report on kilohertz organic complementary inverter driven with surface-grafting conducting polymer electrodes. High device performance, together with the facile patternability and other merits, may promote the application of surface-grafting conducting polymer electrode in the field of organic electronics.

  7. A highly permeable and enhanced surface area carbon-cloth electrode for vanadium redox flow batteries

    NASA Astrophysics Data System (ADS)

    Zhou, X. L.; Zhao, T. S.; Zeng, Y. K.; An, L.; Wei, L.

    2016-10-01

    In this work, a high-performance porous electrode, made of KOH-activated carbon-cloth, is developed for vanadium redox flow batteries (VRFBs). The macro-scale porous structure in the carbon cloth formed by weaving the carbon fibers in an ordered manner offers a low tortuosity (∼1.1) and a broad pore distribution from 5 μm to 100 μm, rendering the electrode a high hydraulic permeability and high effective ionic conductivity, which are beneficial for the electrolyte flow and ion transport through the porous electrode. The use of KOH activation method to create nano-scale pores on the carbon-fiber surfaces leads to a significant increase in the surface area for redox reactions from 2.39 m2 g-1 to 15.4 m2 g-1. The battery assembled with the present electrode delivers an energy efficiency of 80.1% and an electrolyte utilization of 74.6% at a current density of 400 mA cm-2, as opposed to an electrolyte utilization of 61.1% achieved by using a conventional carbon-paper electrode. Such a high performance is mainly attributed to the combination of the excellent mass/ion transport properties and the high surface area rendered by the present electrode. It is suggested that the KOH-activated carbon-cloth electrode is a promising candidate in redox flow batteries.

  8. Enhanced surface production in H{sup -} ion sources by introducing a negatively biased secondary electrode

    SciTech Connect

    An, Young Hwa; Jung, Bong Ki; Hwang, Y. S.

    2010-02-15

    A transformer coupled plasma negative hydrogen ion source with an external rf antenna has been developed at SNU, which is capable of continuous operation with long lifetime. A positively biased plasma electrode (PE) has been successfully used for the optimization of H{sup -} extraction. With molybdenum-coated stainless steel PE, the enhancement of H{sup -} production at the electrode surface was observed at the bias voltage lower than the plasma potential. However, the low bias voltage is unfavorable to H{sup -} beam extraction since the negative ions are repelled. A second electrode is inserted in front of the PE to enhance H{sup -} production at the electrode surface without impeding beam extraction. By biasing the secondary electrode (SE) more negatively, H{sup -} production is clearly enhanced although the SE itself reduces H{sup -} beam currents because of suppressed electron transport in front of the PE. In this configuration enhancement of surface productions is most pronounced in tantalum electrode among various electrode materials.

  9. A Lithographically-Patterned, Elastic Multi-electrode Array for Surface Stimulation of the Spinal Cord

    PubMed Central

    Meacham, Kathleen W.; Giuly, Richard J.; Guo, Liang; Hochman, Shawn; DeWeerth, Stephen P.

    2008-01-01

    A new, scalable process for microfabrication of a silicone-based, elastic multi-electrode array (MEA) is presented. The device is constructed by spinning poly(dimethylsiloxane) (PDMS) silicone elastomer onto a glass slide, depositing and patterning gold to construct wires and electrodes, spinning on a second PDMS layer, and then micropatterning the second PDMS layer to expose electrode contacts. The micropatterning of PDMS involves a custom reactive ion etch (RIE) process that preserves the underlying gold thin film. Once completed, the device can be removed from the glass slide for conformal interfacing with neural tissue. Prototype MEAs feature electrodes smaller than those known to be reported on silicone substrate (60 μm diameter exposed electrode area) and were capable of selectively stimulating the surface of the in vitro isolated spinal cord of the juvenile rat. Stretchable serpentine traces were also incorporated into the functional PDMS-based MEA, and their implementation and testing is described. PMID:17914674

  10. Polymer Coatings of Cochlear Implant Electrode Surface - An Option for Improving Electrode-Nerve-Interface by Blocking Fibroblast Overgrowth.

    PubMed

    Hadler, C; Aliuos, P; Brandes, G; Warnecke, A; Bohlmann, J; Dempwolf, W; Menzel, H; Lenarz, T; Reuter, G; Wissel, K

    2016-01-01

    Overgrowth of connective tissue and scar formation induced by the electrode array insertion increase the impedance and, thus, diminish the interactions between neural probes as like cochlear implants (CI) and the target tissue. Therefore, it is of great clinical interest to modify the carrier material of the electrodes to improve the electrode nerve interface for selective cell adhesion. On one side connective tissue growth needs to be reduced to avoid electrode array encapsulation, on the other side the carrier material should not compromise the interaction with neuronal cells. The present in vitro-study qualitatively and quantitatively characterises the interaction of fibroblasts, glial cells and spiral ganglion neurons (SGN) with ultrathin poly(N,N-dimethylacrylamide) (PDMAA), poly(2-ethyloxazoline) (PEtOx) and poly([2-methacryloyloxy)ethyl]trimethylammoniumchlorid) (PMTA) films immobilised onto glass surfaces using a photoreactive anchor layer. The layer thickness and hydrophilicity of the polymer films were characterised by ellipsometric and water contact angle measurement. Moreover the topography of the surfaces was investigated using atomic force microscopy (AFM). The neuronal and non-neuronal cells were dissociated from spiral ganglions of postnatal rats and cultivated for 48 h on top of the polymer coatings. Immunocytochemical staining of neuronal and intermediary filaments revealed that glial cells predominantly attached on PMTA films, but not on PDMAA and PEtOx monolayers. Hereby, strong survival rates and neurite outgrowth were only found on PMTA, whereas PDMAA and PEtOx coatings significantly reduced the SG neuron survival and neuritogenesis. As also shown by scanning electron microscopy (SEM) SGN strongly survived and retained their differentiated phenotype only on PMTA. In conclusion, survival and neuritogenesis of SGN may be associated with the extent of the glial cell growth. Since PMTA was the only of the polar polymers used in this study bearing

  11. Polymer Coatings of Cochlear Implant Electrode Surface – An Option for Improving Electrode-Nerve-Interface by Blocking Fibroblast Overgrowth

    PubMed Central

    Hadler, C.; Aliuos, P.; Brandes, G.; Warnecke, A.; Bohlmann, J.; Dempwolf, W.; Menzel, H.; Lenarz, T.; Reuter, G.; Wissel, K.

    2016-01-01

    Overgrowth of connective tissue and scar formation induced by the electrode array insertion increase the impedance and, thus, diminish the interactions between neural probes as like cochlear implants (CI) and the target tissue. Therefore, it is of great clinical interest to modify the carrier material of the electrodes to improve the electrode nerve interface for selective cell adhesion. On one side connective tissue growth needs to be reduced to avoid electrode array encapsulation, on the other side the carrier material should not compromise the interaction with neuronal cells. The present in vitro-study qualitatively and quantitatively characterises the interaction of fibroblasts, glial cells and spiral ganglion neurons (SGN) with ultrathin poly(N,N-dimethylacrylamide) (PDMAA), poly(2-ethyloxazoline) (PEtOx) and poly([2-methacryloyloxy)ethyl]trimethylammoniumchlorid) (PMTA) films immobilised onto glass surfaces using a photoreactive anchor layer. The layer thickness and hydrophilicity of the polymer films were characterised by ellipsometric and water contact angle measurement. Moreover the topography of the surfaces was investigated using atomic force microscopy (AFM). The neuronal and non-neuronal cells were dissociated from spiral ganglions of postnatal rats and cultivated for 48 h on top of the polymer coatings. Immunocytochemical staining of neuronal and intermediary filaments revealed that glial cells predominantly attached on PMTA films, but not on PDMAA and PEtOx monolayers. Hereby, strong survival rates and neurite outgrowth were only found on PMTA, whereas PDMAA and PEtOx coatings significantly reduced the SG neuron survival and neuritogenesis. As also shown by scanning electron microscopy (SEM) SGN strongly survived and retained their differentiated phenotype only on PMTA. In conclusion, survival and neuritogenesis of SGN may be associated with the extent of the glial cell growth. Since PMTA was the only of the polar polymers used in this study bearing

  12. Dielectrophoresis-assisted electroconductive polymer-based fabrication of high surface area electrodes

    NASA Astrophysics Data System (ADS)

    Perez-Gonzalez, Victor H.; Ho, Vinh; Kulinsky, Lawrence; Martinez-Chapa, Sergio O.

    2014-03-01

    In this work we present a novel microfabrication process that is based on combined use of dielectrophoresis (DEP) to attract particles or cells to electrodes and to follow this step by an electrodeposition of polypyrrole (PPy) to entrap the particles or cells on electrode surface. This process can be used for mass-production of high surface area structures as well as to the creation of functionally graded materials. DEP was employed to pull the microparticles toward the surface of the electrodes and hold them in place while PPy was electrodeposited. Polystyrene microbeads with diameters ranging from 1 to 10 microns were employed in this study. Experimental results demonstrated that PPy can entrap the particles attracted to the electrode surface by the positive DEP. It was also demonstrated that hierarchical structures can be created where smaller microbeads are attached to, caught and secured on the surface of larger microbeads entrapped on the electrode surface. Furthermore, as DEP can be employed for manipulating of wide variety of polarizable materials, this process can also entrap inorganic and biological microparticles in the fabricated structure. Applications of this work include, but are not limited to, the development of biomedical, electrokinetic, and energy storage devices, electrochemical sensors, and scaffolds.

  13. Controlled carbon nitride growth on surfaces for hydrogen evolution electrodes.

    PubMed

    Shalom, Menny; Gimenez, Sixto; Schipper, Florian; Herraiz-Cardona, Isaac; Bisquert, Juan; Antonietti, Markus

    2014-04-01

    Efficient and low-cost electrocatalysts for the hydrogen evolution reaction are highly desired for future renewable energy systems. Described herein is the reduction of water to hydrogen using a metal-free carbon nitride electrocatalyst which operates in neutral and alkaline environments. An efficient, easy, and general method for growing ordered carbon nitride on different electrodes was developed. The metal-free catalyst demonstrates low overpotential values, which are comparable to those of non-noble metals, with reasonable current densities. The facile deposition method enables the fabrication of many electronic and photoelectronic devices based on carbon nitride for renewable energy applications. PMID:24574144

  14. Conformable actively multiplexed high-density surface electrode array for brain interfacing

    DOEpatents

    Rogers, John; Kim, Dae-Hyeong; Litt, Brian; Viventi, Jonathan

    2015-01-13

    Provided are methods and devices for interfacing with brain tissue, specifically for monitoring and/or actuation of spatio-temporal electrical waveforms. The device is conformable having a high electrode density and high spatial and temporal resolution. A conformable substrate supports a conformable electronic circuit and a barrier layer. Electrodes are positioned to provide electrical contact with a brain tissue. A controller monitors or actuates the electrodes, thereby interfacing with the brain tissue. In an aspect, methods are provided to monitor or actuate spatio-temporal electrical waveform over large brain surface areas by any of the devices disclosed herein.

  15. Direct observation of lanthanide(III)-phthalocyanine molecules on Au(111) by using scanning tunneling microscopy and scanning tunneling spectroscopy and thin-film field-effect transistor properties of Tb(III)- and Dy(III)-phthalocyanine molecules.

    PubMed

    Katoh, Keiichi; Yoshida, Yusuke; Yamashita, Masahiro; Miyasaka, Hitoshi; Breedlove, Brian K; Kajiwara, Takashi; Takaishi, Shinya; Ishikawa, Naoto; Isshiki, Hironari; Zhang, Yan Feng; Komeda, Tadahiro; Yamagishi, Masakazu; Takeya, Jun

    2009-07-29

    The crystal structures of double-decker single molecule magnets (SMM) LnPc(2) (Ln = Tb(III) and Dy(III); Pc = phthalocyanine) and non-SMM YPc(2) were determined by using X-ray diffraction analysis. The compounds are isomorphous to each other. The compounds have metal centers (M = Tb(3+), Dy(3+), and Y(3+)) sandwiched by two Pc ligands via eight isoindole-nitrogen atoms in a square-antiprism fashion. The twist angle between the two Pc ligands is 41.4 degrees. Scanning tunneling microscopy was used to investigate the compounds adsorbed on a Au(111) surface, deposited by using the thermal evaporation in ultrahigh vacuum. Both MPc(2) with eight lobes and MPc with four lobes, which has lost one Pc ligand, were observed. In the scanning tunneling spectroscopy images of TbPc molecules at 4.8 K, a Kondo peak with a Kondo temperature (T(K)) of approximately 250 K was observed near the Fermi level (V = 0 V). On the other hand, DyPc, YPc, and MPc(2) exhibited no Kondo peak. To understand the observed Kondo effect, the energy splitting of sublevels in a crystal field should be taken into consideration. As the next step in our studies on the SMM/Kondo effect in Tb-Pc derivatives, we investigated the electronic transport properties of Ln-Pc molecules as the active layer in top- and bottom-contact thin-film organic field effect transistor devices. Tb-Pc molecule devices exhibit p-type semiconducting properties with a hole mobility (mu(H)) of approximately 10(-4) cm(2) V(-1) s(-1). Interestingly, the Dy-Pc based devices exhibited ambipolar semiconducting properties with an electron mobility (mu(e)) of approximately 10(-5) and a mu(H) of approximately 10(-4) cm(2) V(-1) s(-1). This behavior has important implications for the electronic structure of the molecules. PMID:19569681

  16. Electrochemical decolorization of dye wastewater by surface-activated boron-doped nanocrystalline diamond electrode.

    PubMed

    Chen, Chienhung; Nurhayati, Ervin; Juang, Yaju; Huang, Chihpin

    2016-07-01

    Complex organics contained in dye wastewater are difficult to degrade and often require electrochemical advanced oxidation processes (EAOPs) to treat it. Surface activation of the electrode used in such treatment is an important factor determining the success of the process. The performance of boron-doped nanocrystalline diamond (BD-NCD) film electrode for decolorization of Acid Yellow (AY-36) azo dye with respect to the surface activation by electrochemical polarization was studied. Anodic polarization found to be more suitable as electrode pretreatment compared to cathodic one. After anodic polarization, the originally H-terminated surface of BD-NCD was changed into O-terminated, making it more hydrophilic. Due to the oxidation of surface functional groups and some portion of sp(2) carbon in the BD-NCD film during anodic polarization, the electrode was successfully being activated showing lower background current, wider potential window and considerably less surface activity compared to the non-polarized one. Consequently, electrooxidation (EO) capability of the anodically-polarized BD-NCD to degrade AY-36 dye was significantly enhanced, capable of nearly total decolorization and chemical oxygen demand (COD) removal even after several times of re-using. The BD-NCD film electrode favored acidic condition for the dye degradation; and the presence of chloride ion in the solution was found to be more advantageous than sulfate active species.

  17. Evidence for surface Ag + complexes as the SERS-active sites on Ag electrodes

    NASA Astrophysics Data System (ADS)

    Watanabe, T.; Kawanami, O.; Honda, K.; Pettinger, B.

    1983-12-01

    Evidence is given that SERS-active sites at Ag electrodes are associated with Ag + ions, forming sparingly soluble surface complexes with ligands such as pyridine molecules and halide ions. Such surface Ag + complexes contribute a factor of >800 to the overall (10 7-fold) enhancement, possibly via a resonance Raman effect.

  18. Laser-based surface preparation of composite laminates leads to improved electrodes for electrical measurements

    NASA Astrophysics Data System (ADS)

    Almuhammadi, Khaled; Selvakumaran, Lakshmi; Alfano, Marco; Yang, Yang; Bera, Tushar Kanti; Lubineau, Gilles

    2015-12-01

    Electrical impedance tomography (EIT) is a low-cost, fast and effective structural health monitoring technique that can be used on carbon fiber reinforced polymers (CFRP). Electrodes are a key component of any EIT system and as such they should feature low resistivity as well as high robustness and reproducibility. Surface preparation is required prior to bonding of electrodes. Currently this task is mostly carried out by traditional sanding. However this is a time consuming procedure which can also induce damage to surface fibers and lead to spurious electrode properties. Here we propose an alternative processing technique based on the use of pulsed laser irradiation. The processing parameters that result in selective removal of the electrically insulating resin with minimum surface fiber damage are identified. A quantitative analysis of the electrical contact resistance is presented and the results are compared with those obtained using sanding.

  19. Three-Dimensional Adhesion Map Based on Surface and Interfacial Cutting Analysis System for Predicting Adhesion Properties of Composite Electrodes.

    PubMed

    Kim, Kyuman; Byun, Seoungwoo; Cho, Inseong; Ryou, Myung-Hyun; Lee, Yong Min

    2016-09-14

    Using a surface and interfacial cutting analysis system (SAICAS) that can measure the adhesion strength of a composite electrode at a specific depth from the surface, we can subdivide the adhesion strength of a composite electrode into two classes: (1) the adhesion strength between the Al current collector and the cathode composite electrode (FAl-Ca) and (2) the adhesion strength measured at the mid-depth of the cathode composite electrode (Fmid). Both adhesion strengths, FAl-Ca and Fmid, increase with increasing electrode density and loading level. From the SAICAS measurement, we obtain a mathematical equation that governs the adhesion strength of the composite electrodes. This equation revealed a maximum accuracy of 97.2% and 96.1% for FAl-Ca and Fmid, respectively, for four randomly chosen composite electrodes varying in electrode density and loading level. PMID:27398829

  20. Low temperature formation of electrode having electrically conductive metal oxide surface

    DOEpatents

    Anders, Simone; Anders, Andre; Brown, Ian G.; McLarnon, Frank R.; Kong, Fanping

    1998-01-01

    A low temperature process is disclosed for forming metal suboxides on substrates by cathodic arc deposition by either controlling the pressure of the oxygen present in the deposition chamber, or by controlling the density of the metal flux, or by a combination of such adjustments, to thereby control the ratio of oxide to metal in the deposited metal suboxide coating. The density of the metal flux may, in turn, be adjusted by controlling the discharge current of the arc, by adjusting the pulse length (duration of on cycle) of the arc, and by adjusting the frequency of the arc, or any combination of these parameters. In a preferred embodiment, a low temperature process is disclosed for forming an electrically conductive metal suboxide, such as, for example, an electrically conductive suboxide of titanium, on an electrode surface, such as the surface of a nickel oxide electrode, by such cathodic arc deposition and control of the deposition parameters. In the preferred embodiment, the process results in a titanium suboxide-coated nickel oxide electrode exhibiting reduced parasitic evolution of oxygen during charging of a cell made using such an electrode as the positive electrode, as well as exhibiting high oxygen overpotential, resulting in suppression of oxygen evolution at the electrode at full charge of the cell.

  1. Surface modification of neural recording electrodes with conducting polymer/biomolecule blends.

    PubMed

    Cui, X; Lee, V A; Raphael, Y; Wiler, J A; Hetke, J F; Anderson, D J; Martin, D C

    2001-08-01

    The interface between micromachined neural microelectrodes and neural tissue plays an important role in chronic in vivo recording. Electrochemical polymerization was used to optimize the surface of the metal electrode sites. Electrically conductive polymers (polypyrrole) combined with biomolecules having cell adhesion functionality were deposited with great precision onto microelectrode sites of neural probes. The biomolecules used were a silk-like polymer having fibronectin fragments (SLPF) and nonapeptide CDPGYIGSR. The existence of protein polymers and peptides in the coatings was confirmed by reflective microfocusing Fourier transform infrared spectroscopy (FTIR). The morphology of the coating was rough and fuzzy, providing a high density of bioactive sites for interaction with neural cells. This high interfacial area also helped to lower the impedance of the electrode site and, consequently, to improve the signal transport. Impedance spectroscopy showed a lowered magnitude and phase of impedance around the biologically relevant frequency of 1 kHz. Cyclic voltammetry demonstrated the intrinsic redox reaction of the doped polypyrrole and the increased charge capacity of the coated electrodes. Rat glial cells and human neuroblastoma cells were seeded and cultured on neural probes with coated and uncoated electrodes. Glial cells appeared to attach better to polypyrrole/SLPF-coated electrodes than to uncoated gold electrodes. Neuroblastoma cells grew preferentially on and around the polypyrrole/CDPGYIGSR-coated electrode sites while the polypyrrole/CH(3)COO(-)-coated sites on the same probe did not show a preferential attraction to the cells. These results indicate that we can adjust the chemical composition, morphology, electronic transport, and bioactivity of polymer coatings on electrode surfaces on a multichannel micromachined neural probe by controlling electrochemical deposition conditions.

  2. Generalized Butler-Volmer relation on a curved electrode surface under the action of stress

    NASA Astrophysics Data System (ADS)

    Yang, FuQian

    2016-11-01

    According to the principle of thermal activation process, the energy state of a material under the action of stress is a function of local stress. A generalized Butler-Volmer relationship for the electrode reaction on the surface of a curved electrode is derived, which takes account of the effects of local stress and the radius of mean curvature. From this relationship, the overpotential is found to be proportional to hydrostatic stress and the activation volume under the condition of open circuit. The conditions for the deposition of the material made solely from solute atoms and the formation of surface pits and porous structures are obtained, using the generalized Butler-Volmer relationship.

  3. The surface chemistry of lithium electrodes in alkyl carbonate solutions

    SciTech Connect

    Aurbach, D.; Ein-Ely, Y.; Zaban, A.

    1994-01-01

    The chemical composition of the surface films formed on lithium in alkyl carbonate solutions was explored using surface sensitive Fourier transform infrared spectroscopy (external reflectance mode). The solvents included propylene carbonate, ethylene carbonate, and dimethyl carbonate. The salts included LiAsF{sub 6}, LiClO{sub 4}, LiBF{sub 4}, and LiPF{sub 6}. The advantages of this work over previous studies are that highly reflective Li surfaces were prepared fresh in solution and that the aging processes of the surface films initially formed could be rigorously investigated. Furthermore these three important solvents were investigated in a single study. This work further proves that the films initially formed on Li surfaces in these solvents consist of ROCO{sub 2}Li as the major constituents. Upon storage, the films initially formed react with trace water to form Li{sub 2}CO{sub 3}, which gradually also becomes a major surface species. It was found that these aging processes also depend on the salts used (for example ROCO{sub 2}Li or Li{sub 2}CO{sub 3} films are not stable in LiPF{sub 6} or LiBF{sub 4} solutions).

  4. Sequence and Temperature Influence on Kinetics of DNA Strand Displacement at Gold Electrode Surfaces.

    PubMed

    Biala, Katarzyna; Sedova, Ada; Flechsig, Gerd-Uwe

    2015-09-16

    Understanding complex contributions of surface environment to tethered nucleic acid sensing experiments has proven challenging, yet it is important because it is essential for interpretation and calibration of indispensable methods, such as microarrays. We investigate the effects of DNA sequence and solution temperature gradients on the kinetics of strand displacement at heated gold wire electrodes, and at gold disc electrodes in a heated solution. Addition of a terminal double mismatch (toehold) provides a reduction in strand displacement energy barriers sufficient to probe the secondary mechanisms involved in the hybridization process. In four different DNA capture probe sequences (relevant for the identification of genetically modified maize MON810), all but one revealed a high activation energy up to 200 kJ/mol during hybridization, that we attribute to displacement of protective strands by capture probes. Protective strands contain 4 to 5 mismatches to ease their displacement by the surface-confined probes at the gold electrodes. A low activation energy (30 kJ/mol) was observed for the sequence whose protective strand contained a toehold and one central mismatch, its kinetic curves displayed significantly different shapes, and we observed a reduced maximum signal intensity as compared to other sequences. These findings point to potential sequence-related contributions to oligonucleotide diffusion influencing kinetics. Additionally, for all sequences studied with heated wire electrodes, we observed a 23 K lower optimal hybridization temperature in comparison with disc electrodes in heated solution, and greatly reduced voltammetric signals after taking into account electrode surface area. We propose that thermodiffusion due to temperature gradients may influence both hybridization and strand displacement kinetics at heated microelectrodes, an explanation supported by computational fluid dynamics. DNA assays with surface-confined capture probes and temperature

  5. Assessment of Carbon/Salt/Adhesive Electrodes for Surface Electromyography Measurements

    PubMed Central

    Posada-Quintero, Hugo; Rood, Ryan; Burnham, Ken; Pennace, John

    2016-01-01

    This paper presents the evaluation of novel electrodes for surface electromyography (sEMG) measurements. The electrodes are based on the mixture of carbon powder, quaternary salt, and viscoelastic polymeric adhesive (carbon/salt/adhesive or simply CSA), which when combined, provide the unique advantages of having longer (theoretically infinite) shelf life and potentially lower cost than Ag/AgCl hydrogel electrodes, consistent with FLEXcon’s Patent #8 673 184. The 20 subjects were recruited to collect simultaneous recordings of sEMG signals using Ag/AgCl and CSA electrodes, side-by-side on triceps brachii, tibial anterior muscles, biceps brachii, and quadriceps femoris. Although CSA sEMG electrodes showed higher electrode-skin contact impedance for the frequency range of 4 Hz–2 kHz, no significant differences were found in the signals’ amplitude between the two electrodes either during relaxation or contraction stages. Furthermore, correlations of the computed linear envelopes (>0.91), rms value envelopes (>0.91), and power spectral densities (>0.95) of the signals were found to be high between the two media. Detected ON- and OFF-times of contraction were also highly correlated (>0.9) and interchangeable (ON-time: bias = −0.02, variance = 0.11; OFF-time: bias = −0.04, variance = 0.23) between the two media. However, CSA sEMG electrodes exhibited a significantly better response to noise (38.3 ± 10.6 dB versus 32.7 ± 15.6 dB) and motion artifacts (24.1 ± 12.1 dB versus 16.6 ± 8.52 dB), and a significantly lower spectral deformation (1.32 ± 0.2 versus 1.46 ± 0.4). Ag/AgCl electrodes showed a significantly more peaked and sensitive response to EMG amplitude (67.9 ± 13.9 dB versus 65.4 ± 14.6 dB). Given no significant differences in many of the measures described earlier and the fact that CSA electrodes have an infinite shelf-life are potentially lower cost, and are more resistant to motion artifacts, the new electrodes provide an attractive alternative

  6. Assessment of Carbon/Salt/Adhesive Electrodes for Surface Electromyography Measurements.

    PubMed

    Posada-Quintero, Hugo; Rood, Ryan; Burnham, Ken; Pennace, John; Chon, Ki

    2016-01-01

    This paper presents the evaluation of novel electrodes for surface electromyography (sEMG) measurements. The electrodes are based on the mixture of carbon powder, quaternary salt, and viscoelastic polymeric adhesive (carbon/salt/adhesive or simply CSA), which when combined, provide the unique advantages of having longer (theoretically infinite) shelf life and potentially lower cost than Ag/AgCl hydrogel electrodes, consistent with FLEXcon's Patent #8 673 184. The 20 subjects were recruited to collect simultaneous recordings of sEMG signals using Ag/AgCl and CSA electrodes, side-by-side on triceps brachii, tibial anterior muscles, biceps brachii, and quadriceps femoris. Although CSA sEMG electrodes showed higher electrode-skin contact impedance for the frequency range of 4 Hz-2 kHz, no significant differences were found in the signals' amplitude between the two electrodes either during relaxation or contraction stages. Furthermore, correlations of the computed linear envelopes (>0.91), rms value envelopes (>0.91), and power spectral densities (>0.95) of the signals were found to be high between the two media. Detected ON- and OFF-times of contraction were also highly correlated (>0.9) and interchangeable (ON-time: bias = -0.02, variance = 0.11; OFF-time: bias = -0.04, variance = 0.23) between the two media. However, CSA sEMG electrodes exhibited a significantly better response to noise (38.3 ± 10.6 dB versus 32.7 ± 15.6 dB) and motion artifacts (24.1 ± 12.1 dB versus 16.6 ± 8.52 dB), and a significantly lower spectral deformation (1.32 ± 0.2 versus 1.46 ± 0.4). Ag/AgCl electrodes showed a significantly more peaked and sensitive response to EMG amplitude (67.9 ± 13.9 dB versus 65.4 ± 14.6 dB). Given no significant differences in many of the measures described earlier and the fact that CSA electrodes have an infinite shelf-life are potentially lower cost, and are more resistant to motion artifacts, the new electrodes provide an attractive alternative to Ag

  7. Assessment of Carbon/Salt/Adhesive Electrodes for Surface Electromyography Measurements.

    PubMed

    Posada-Quintero, Hugo; Rood, Ryan; Burnham, Ken; Pennace, John; Chon, Ki

    2016-01-01

    This paper presents the evaluation of novel electrodes for surface electromyography (sEMG) measurements. The electrodes are based on the mixture of carbon powder, quaternary salt, and viscoelastic polymeric adhesive (carbon/salt/adhesive or simply CSA), which when combined, provide the unique advantages of having longer (theoretically infinite) shelf life and potentially lower cost than Ag/AgCl hydrogel electrodes, consistent with FLEXcon's Patent #8 673 184. The 20 subjects were recruited to collect simultaneous recordings of sEMG signals using Ag/AgCl and CSA electrodes, side-by-side on triceps brachii, tibial anterior muscles, biceps brachii, and quadriceps femoris. Although CSA sEMG electrodes showed higher electrode-skin contact impedance for the frequency range of 4 Hz-2 kHz, no significant differences were found in the signals' amplitude between the two electrodes either during relaxation or contraction stages. Furthermore, correlations of the computed linear envelopes (>0.91), rms value envelopes (>0.91), and power spectral densities (>0.95) of the signals were found to be high between the two media. Detected ON- and OFF-times of contraction were also highly correlated (>0.9) and interchangeable (ON-time: bias = -0.02, variance = 0.11; OFF-time: bias = -0.04, variance = 0.23) between the two media. However, CSA sEMG electrodes exhibited a significantly better response to noise (38.3 ± 10.6 dB versus 32.7 ± 15.6 dB) and motion artifacts (24.1 ± 12.1 dB versus 16.6 ± 8.52 dB), and a significantly lower spectral deformation (1.32 ± 0.2 versus 1.46 ± 0.4). Ag/AgCl electrodes showed a significantly more peaked and sensitive response to EMG amplitude (67.9 ± 13.9 dB versus 65.4 ± 14.6 dB). Given no significant differences in many of the measures described earlier and the fact that CSA electrodes have an infinite shelf-life are potentially lower cost, and are more resistant to motion artifacts, the new electrodes provide an attractive alternative to Ag

  8. Chemically modified electrodes by nucleophilic substitution of chlorosilylated platinum oxide surfaces

    NASA Astrophysics Data System (ADS)

    Chen, Chun-Hsien; Hutchison, James H.; Postlethwaite, Timothy A.; Richardson, John N.; Murray, R. W.

    1994-07-01

    Chlorosilylated platinum oxide electrode surfaces can be generated by reaction of SiCl4 vapor with an electrochemically prepared monolayer of platinum oxide. A variety of nucleophilic agents (such as alcohols, amines, thiols, and Grignard reagents) can be used to displace chloride and thereby functionalize the metal surface. Electroactive surfaces prepared with ferrocene methanol as the nucleophile show that derivatization by small molecules can achieve coverages on the order of a full monolayer. Surfaces modified with long-chain alkyl groups efficiently block electrode reactions of redox probes dissolved in the contacting solution, but other electrochemical (double layer capacitance and surface coverage) and contact angle measurements suggest that these molecule films are not highly ordered, self-assembled monolayers.

  9. Shaping of steel mold surface of lens array by electrical discharge machining with spherical ball electrode.

    PubMed

    Takino, Hideo; Hosaka, Takahiro

    2016-06-20

    We propose a method for fabricating a spherical lens array mold by electrical discharge machining (EDM) with a ball-type electrode. The electrode is constructed by arranging conductive spherical balls in an array. To fundamentally examine the applicability of the proposed EDM method to the fabrication of lens array molds, we use an electrode having a single ball to shape a lens array mold made of stainless steel with 16 spherical elements, each having a maximum depth of 0.5 mm. As a result, a mold surface is successfully shaped with a peak-to-valley shape accuracy of approximately 10 μm, and an average surface roughness of 0.85 μm. PMID:27409126

  10. Shaping of steel mold surface of lens array by electrical discharge machining with spherical ball electrode.

    PubMed

    Takino, Hideo; Hosaka, Takahiro

    2016-06-20

    We propose a method for fabricating a spherical lens array mold by electrical discharge machining (EDM) with a ball-type electrode. The electrode is constructed by arranging conductive spherical balls in an array. To fundamentally examine the applicability of the proposed EDM method to the fabrication of lens array molds, we use an electrode having a single ball to shape a lens array mold made of stainless steel with 16 spherical elements, each having a maximum depth of 0.5 mm. As a result, a mold surface is successfully shaped with a peak-to-valley shape accuracy of approximately 10 μm, and an average surface roughness of 0.85 μm.

  11. Lactose electroisomerization into lactulose: effect of the electrode material, active membrane surface area-to-electrode surface area ratio, and interelectrode-membrane distance.

    PubMed

    Aït-Aissa, Amara; Aïder, Mohammed

    2014-01-01

    The aim of the present work was to study and develop an innovative, clean, and environmentally friendly process for lactulose synthesis by electroactivation of lactose. In this work, the electrode material (type 304 stainless steel, titanium, and copper), dimensionless interelectrode-membrane distance at the cathodic compartment (0.36, 0.68, and 1), and the membrane:electrode surface area ratio (0.23, 0.06, and 0.015) were considered to be the factors that could affect the kinetic conversion of lactose into lactulose. The reactions were conducted under an initial lactose concentration of 0.15mol/L at 10°C, Froude number (mixing speed) of 2.05×10(-2), and electric current intensity of 300mA for 30min. The highest lactulose formation yield of 32.50% (0.05mol/L) was obtained by using a copper electrode, interelectrode-membrane distance of 0.36, and membrane:electrode surface area ratio of 0.23. The 2-parameter Langmuir, Freundlich, and Temkin isotherm models were used for the prediction of the lactose isomerization kinetics as well as the 3-parameter Langmuir-Freundlich isotherm model. It was shown that the lactose isomerization kinetics into lactulose followed the Temkin and Langmuir-Freundlich models with coefficients of determination of 0.99 and 0.90 and a relative error of 1.42 to 1.56% and 4.27 to 4.37%, respectively. PMID:24931526

  12. High Surface Area Electrodes Derived from Polymer Wrapped Carbon Nanotubes for Enhanced Energy Storage Devices.

    PubMed

    Bakhtiary Davijani, Amir A; Liu, H Clive; Gupta, Kishor; Kumar, Satish

    2016-09-21

    Electrical double layer capacitors store energy on two adjacent layers, resulting in fast charging and discharging, but their energy density is limited by the available surface area. In this study, using poly(methyl methacrylate) assisted sonication, carbon nanotube buckypapers with specific surface area as high as 950 m(2)/g have been processed. Performance of these high surface area buckypapers have been evaluated as supercapacitor electrodes. The energy density of these high surface area electrodes at low power density of 0.68 kW/kg was 22.3 Wh/kg, and at high power density of 84 kW/kg was 3.13 Wh/kg using the ionic liquid electrolyte. PMID:27556746

  13. High Surface Area Electrodes Derived from Polymer Wrapped Carbon Nanotubes for Enhanced Energy Storage Devices.

    PubMed

    Bakhtiary Davijani, Amir A; Liu, H Clive; Gupta, Kishor; Kumar, Satish

    2016-09-21

    Electrical double layer capacitors store energy on two adjacent layers, resulting in fast charging and discharging, but their energy density is limited by the available surface area. In this study, using poly(methyl methacrylate) assisted sonication, carbon nanotube buckypapers with specific surface area as high as 950 m(2)/g have been processed. Performance of these high surface area buckypapers have been evaluated as supercapacitor electrodes. The energy density of these high surface area electrodes at low power density of 0.68 kW/kg was 22.3 Wh/kg, and at high power density of 84 kW/kg was 3.13 Wh/kg using the ionic liquid electrolyte.

  14. Surface oxide growth on platinum electrode in aqueous trifluoromethanesulfonic acid.

    PubMed

    Furuya, Yoshihisa; Mashio, Tetsuya; Ohma, Atsushi; Dale, Nilesh; Oshihara, Kenzo; Jerkiewicz, Gregory

    2014-10-28

    Platinum in the form of nanoparticles is the key and most expensive component of polymer electrolyte membrane fuel cells, while trifluoromethanesulfonic acid (CF3SO3H) is the smallest fluorinated sulfonic acid. Nafion, which acts as both electrolyte and separator in fuel cells, contains -CF2SO3H groups. Consequently, research on the electrochemical behaviour of Pt in aqueous CF3SO3H solutions creates important background knowledge that can benefit fuel cell development. In this contribution, Pt electro-oxidation is studied in 0.1 M aqueous CF3SO3H as a function of the polarization potential (E(p), 1.10 ≤ E(p) ≤ 1.50 V), polarization time (t(p), 10(0) ≤ t(p) ≤ 10(4) s), and temperature (T, 278 ≤ T ≤ 333 K). The critical thicknesses (X1), which determines the applicability of oxide growth theories, is determined and related to the oxide thickness (d(ox)). Because X1 > d(ox) for the entire range of E(p), t(p), and T values, the formation of Pt surface oxide follows the interfacial place-exchange or the metal cation escape mechanism. The mechanism of Pt electro-oxidation is revised and expanded by taking into account possible interactions of cations, anions, and water molecules with Pt. A modified kinetic equation for the interfacial place exchange is proposed. The application of the interfacial place-exchange and metal cation escape mechanisms leads to an estimation of the Pt(δ+)-O(δ-) surface dipole (μ(PtO)), and the potential drop (V(ox)) and electric field (E(ox)) within the oxide. The Pt-anion interactions affect the oxidation kinetics by indirectly influencing the electric field within the double layer and the surface oxide. PMID:25362330

  15. Surface oxide growth on platinum electrode in aqueous trifluoromethanesulfonic acid

    NASA Astrophysics Data System (ADS)

    Furuya, Yoshihisa; Mashio, Tetsuya; Ohma, Atsushi; Dale, Nilesh; Oshihara, Kenzo; Jerkiewicz, Gregory

    2014-10-01

    Platinum in the form of nanoparticles is the key and most expensive component of polymer electrolyte membrane fuel cells, while trifluoromethanesulfonic acid (CF3SO3H) is the smallest fluorinated sulfonic acid. Nafion, which acts as both electrolyte and separator in fuel cells, contains -CF2SO3H groups. Consequently, research on the electrochemical behaviour of Pt in aqueous CF3SO3H solutions creates important background knowledge that can benefit fuel cell development. In this contribution, Pt electro-oxidation is studied in 0.1 M aqueous CF3SO3H as a function of the polarization potential (Ep, 1.10 ≤ Ep ≤ 1.50 V), polarization time (tp, 100 ≤ tp ≤ 104 s), and temperature (T, 278 ≤ T ≤ 333 K). The critical thicknesses (X1), which determines the applicability of oxide growth theories, is determined and related to the oxide thickness (dox). Because X1 > dox for the entire range of Ep, tp, and T values, the formation of Pt surface oxide follows the interfacial place-exchange or the metal cation escape mechanism. The mechanism of Pt electro-oxidation is revised and expanded by taking into account possible interactions of cations, anions, and water molecules with Pt. A modified kinetic equation for the interfacial place exchange is proposed. The application of the interfacial place-exchange and metal cation escape mechanisms leads to an estimation of the Ptδ+-Oδ- surface dipole (μPtO), and the potential drop (Vox) and electric field (Eox) within the oxide. The Pt-anion interactions affect the oxidation kinetics by indirectly influencing the electric field within the double layer and the surface oxide.

  16. Surface-enhanced raman scattering from ethylenediaminetetraacetic-disodium salt and nitrate ions on silver electrodes

    NASA Astrophysics Data System (ADS)

    Wetzel, H.; Pettinger, B.; Wenning, U.

    1980-10-01

    Surface-enhanced Raman scattering (SERS) from ethylenediaminetetraacetic-disodium salt adsorbed on silver electrodes has been obtained for the 913, 935 and 1408 cm -1 modes. Addition of this salt to NaNO 3 solutions leads to an enhancement of the NO -3 band at 1050 cm -1. Oxidation/reduction cycles leading to surface roughening and a photochemical reaction caused by the exciting light are prerequisites for these enhancements. The SER signal can irreversibly be quenched by cathodic polarisation.

  17. Benchmark investigation of diamondoid-functionalized electrodes for nanopore DNA sequencing.

    PubMed

    Sivaraman, Ganesh; Amorim, Rodrigo G; Scheicher, Ralph H; Fyta, Maria

    2016-10-14

    Small diamond-like particles, diamondoids, have been shown to effectively functionalize gold electrodes in order to sense DNA units passing between the nanopore-embedded electrodes. In this work, we present a comparative study of Au(111) electrodes functionalized with different derivatives of lower diamondoids. Focus is put on the electronic and transport properties of such electrodes for different DNA nucleotides placed within the electrode gap. The functionalization promotes a specific binding to DNA leading to different properties for the system, which provides a tool set to systematically improve the signal-to-noise ratio of the electronic measurements across the electrodes. Using quantum transport calculations, we compare the effectiveness of the different functionalized electrodes in distinguishing the four DNA nucleotides. Our results point to the most effective diamondoid functionalization of gold electrodes in view of biosensing applications. PMID:27607107

  18. Benchmark investigation of diamondoid-functionalized electrodes for nanopore DNA sequencing

    NASA Astrophysics Data System (ADS)

    Sivaraman, Ganesh; Amorim, Rodrigo G.; Scheicher, Ralph H.; Fyta, Maria

    2016-10-01

    Small diamond-like particles, diamondoids, have been shown to effectively functionalize gold electrodes in order to sense DNA units passing between the nanopore-embedded electrodes. In this work, we present a comparative study of Au(111) electrodes functionalized with different derivatives of lower diamondoids. Focus is put on the electronic and transport properties of such electrodes for different DNA nucleotides placed within the electrode gap. The functionalization promotes a specific binding to DNA leading to different properties for the system, which provides a tool set to systematically improve the signal-to-noise ratio of the electronic measurements across the electrodes. Using quantum transport calculations, we compare the effectiveness of the different functionalized electrodes in distinguishing the four DNA nucleotides. Our results point to the most effective diamondoid functionalization of gold electrodes in view of biosensing applications.

  19. Benchmark investigation of diamondoid-functionalized electrodes for nanopore DNA sequencing.

    PubMed

    Sivaraman, Ganesh; Amorim, Rodrigo G; Scheicher, Ralph H; Fyta, Maria

    2016-10-14

    Small diamond-like particles, diamondoids, have been shown to effectively functionalize gold electrodes in order to sense DNA units passing between the nanopore-embedded electrodes. In this work, we present a comparative study of Au(111) electrodes functionalized with different derivatives of lower diamondoids. Focus is put on the electronic and transport properties of such electrodes for different DNA nucleotides placed within the electrode gap. The functionalization promotes a specific binding to DNA leading to different properties for the system, which provides a tool set to systematically improve the signal-to-noise ratio of the electronic measurements across the electrodes. Using quantum transport calculations, we compare the effectiveness of the different functionalized electrodes in distinguishing the four DNA nucleotides. Our results point to the most effective diamondoid functionalization of gold electrodes in view of biosensing applications.

  20. On the interfacial capacitance of an electrolyte at a metallic electrode around zero surface charge

    NASA Astrophysics Data System (ADS)

    Bari Bhuiyan, Lutful; Lamperski, Stanisław

    2013-03-01

    The behaviour of the capacitance of a planar double layer containing a restricted primitive model electrolyte (equi-sized rigid ions moving in a continuum dielectric) at and around zero surface charge is examined for a polarizable electrode with particular emphasis on a metallic surface. Capacitance results are reported for symmetric valency (1:1) salts encompassing a range of concentrations and temperatures covering both electrolyte solution and ionic liquid regimes. Although the modified Poisson-Boltzmann theory is principally employed, at higher concentrations the theoretical calculations have been supplemented by Monte Carlo simulations. Capacitance anomaly, that is, increase of capacitance with temperature at low temperatures, is seen to occur when the electrode is an insulator with a low dielectric constant or when it is unpolarized. No capacitance anomaly is, however, seen for a metallic electrode with an infinite dielectric constant and in this situation the capacitance increases (a) dramatically at low temperatures (strong coupling) at a given concentration, and (b) as concentration increases at a given temperature. These capacitance trends are consistent with earlier works in the presence or absence of surface polarization and, in particular, the results for a conducting electrode at ionic liquid concentrations are consistent with that recently reported by Loth et al. [Phys. Rev. E, 82, 056102 (2010)]. Overall the theoretical predictions are qualitative to semi-quantitative with the simulations.

  1. Polymerization of polypyrrole on single crystal platinum electrodes: a surface structure sensitive reaction.

    PubMed

    Suarez-Herrera, Marco F; Feliu, Juan M

    2008-12-14

    This communication shows experimental results that clearly demonstrated the influence of the crystalline surface structure of the platinum electrode on the early stages of the electropolymerization of pyrrole in aqueous media. The platinum surface structure determines adhesion, coverage level, charge transfer properties as well as bulk properties of the synthesized film like morphology and the ion exchange kinetics during its reduction and oxidation. It is proven that the Pt(110) an Pt(111) surfaces are more suitable for obtain polypyrrole films with higher conductivity and charge-storage capacity than the Pt(100) surface. PMID:19030598

  2. Metal-mesh based transparent electrode on a 3-D curved surface by electrohydrodynamic jet printing

    NASA Astrophysics Data System (ADS)

    Seong, Baekhoon; Yoo, Hyunwoong; Dat Nguyen, Vu; Jang, Yonghee; Ryu, Changkook; Byun, Doyoung

    2014-09-01

    Invisible Ag mesh transparent electrodes (TEs), with a width of 7 μm, were prepared on a curved glass surface by electrohydrodynamic (EHD) jet printing. With a 100 μm pitch, the EHD jet printed the Ag mesh on the convex glass which had a sheet resistance of 1.49 Ω/□. The printing speed was 30 cm s-1 using Ag ink, which had a 10 000 cPs viscosity and a 70 wt% Ag nanoparticle concentration. We further showed the performance of a 3-D transparent heater using the Ag mesh transparent electrode. The EHD jet printed an invisible Ag grid transparent electrode with good electrical and optical properties with promising applications on printed optoelectronic devices.

  3. Surface structured platinum electrodes for the electrochemical reduction of carbon dioxide in imidazolium based ionic liquids.

    PubMed

    Hanc-Scherer, Florin A; Montiel, Miguel A; Montiel, Vicente; Herrero, Enrique; Sánchez-Sánchez, Carlos M

    2015-10-01

    The direct CO2 electrochemical reduction on model platinum single crystal electrodes Pt(hkl) is studied in [C2mim(+)][NTf2(-)], a suitable room temperature ionic liquid (RTIL) medium due to its moderate viscosity, high CO2 solubility and conductivity. Single crystal electrodes represent the most convenient type of surface structured electrodes for studying the impact of RTIL ion adsorption on relevant electrocatalytic reactions, such as surface sensitive electrochemical CO2 reduction. We propose here based on cyclic voltammetry and in situ electrolysis measurements, for the first time, the formation of a stable adduct [C2mimH-CO2(-)] by a radical-radical coupling after the simultaneous reduction of CO2 and [C2mim(+)]. It means between the CO2 radical anion and the radical formed from the reduction of the cation [C2mim(+)] before forming the corresponding electrogenerated carbene. This is confirmed by the voltammetric study of a model imidazolium-2-carboxylate compound formed following the carbene pathway. The formation of that stable adduct [C2mimH-CO2(-)] blocks CO2 reduction after a single electron transfer and inhibits CO2 and imidazolium dimerization reactions. However, the electrochemical reduction of CO2 under those conditions provokes the electrochemical cathodic degradation of the imidazolium based RTIL. This important limitation in CO2 recycling by direct electrochemical reduction is overcome by adding a strong acid, [H(+)][NTf2(-)], into solution. Then, protons become preferentially adsorbed on the electrode surface by displacing the imidazolium cations and inhibiting their electrochemical reduction. This fact allows the surface sensitive electro-synthesis of HCOOH from CO2 reduction in [C2mim(+)][NTf2(-)], with Pt(110) being the most active electrode studied.

  4. Surface structured platinum electrodes for the electrochemical reduction of carbon dioxide in imidazolium based ionic liquids.

    PubMed

    Hanc-Scherer, Florin A; Montiel, Miguel A; Montiel, Vicente; Herrero, Enrique; Sánchez-Sánchez, Carlos M

    2015-10-01

    The direct CO2 electrochemical reduction on model platinum single crystal electrodes Pt(hkl) is studied in [C2mim(+)][NTf2(-)], a suitable room temperature ionic liquid (RTIL) medium due to its moderate viscosity, high CO2 solubility and conductivity. Single crystal electrodes represent the most convenient type of surface structured electrodes for studying the impact of RTIL ion adsorption on relevant electrocatalytic reactions, such as surface sensitive electrochemical CO2 reduction. We propose here based on cyclic voltammetry and in situ electrolysis measurements, for the first time, the formation of a stable adduct [C2mimH-CO2(-)] by a radical-radical coupling after the simultaneous reduction of CO2 and [C2mim(+)]. It means between the CO2 radical anion and the radical formed from the reduction of the cation [C2mim(+)] before forming the corresponding electrogenerated carbene. This is confirmed by the voltammetric study of a model imidazolium-2-carboxylate compound formed following the carbene pathway. The formation of that stable adduct [C2mimH-CO2(-)] blocks CO2 reduction after a single electron transfer and inhibits CO2 and imidazolium dimerization reactions. However, the electrochemical reduction of CO2 under those conditions provokes the electrochemical cathodic degradation of the imidazolium based RTIL. This important limitation in CO2 recycling by direct electrochemical reduction is overcome by adding a strong acid, [H(+)][NTf2(-)], into solution. Then, protons become preferentially adsorbed on the electrode surface by displacing the imidazolium cations and inhibiting their electrochemical reduction. This fact allows the surface sensitive electro-synthesis of HCOOH from CO2 reduction in [C2mim(+)][NTf2(-)], with Pt(110) being the most active electrode studied. PMID:26307480

  5. Autocatalysis by the intermediate surface hydroxide formed during hydrogen peroxide reduction on silver electrodes

    NASA Astrophysics Data System (ADS)

    Doblhofer, K.; Flätgen, G.; Horswell, S.; Pettinger, B.; Wasle, S.; Weil, K. G.

    2009-06-01

    Recent electrochemical studies of the cathodic reduction of hydrogen peroxide (H 2O 2) on silver electrodes in acidic electrolyte (HClO 4) revealed a novel autocatalytic reaction path. Adsorbed hydroxyl groups, OH ad, were proposed to act as the catalyst. To gather further clarity about this mechanism, in particular about the presence and nature of the postulated adsorbate OH ad, in the present work surface science experiments on Ag(1 1 1) electrodes are evaluated. It is concluded that the species OH ad is identical with the surface AgOH formed in alkaline solution as a relatively stable intermediate in the anodic oxidation of OH - to surface-Ag 2O.

  6. Diamond detectors with laser induced surface graphite electrodes

    NASA Astrophysics Data System (ADS)

    Komlenok, M.; Bolshakov, A.; Ralchenko, V.; Konov, V.; Conte, G.; Girolami, M.; Oliva, P.; Salvatori, S.

    2016-11-01

    We report on the response of metal-less CVD polycrystalline-diamond pixel sensors under β-particles irradiation. A 21×21 array of 0.18×0.18 mm2 pixels was realized on one side of a 10.0×10.0×0.5 mm3 polycrystalline diamond substrate by means of laser induced surface graphitization. With the same technique, a large graphite contact, used for detector biasing, was fabricated on the opposite side. A coincidence detecting method was used with two other reference polycrystalline diamond detectors for triggering, instead of commonly used scintillators, positioned in the front and on the back of the sensor-array with respect to the impinging particles trajectory. The collected charge distribution at each pixel was analyzed as a function of the applied bias. No change in the pulse height distribution was recorded by inverting the bias voltage polarity, denoting contacts ohmicity and symmetry. A fairly good pixel response uniformity was obtained: the collected charge most probable value saturates for all the pixels at an electric field strength of about ±0.6 V/μm. Under saturation condition, the average collected charge was equal to =1.64±0.02 fC, implying a charge collection distance of about 285 μm. A similar result, within 2%, was also obtained for 400 MeV electrons at beam test facility at INFN Frascati National Laboratory. Experimental results highlighted that more than 84% of impinging particles involved only one pixel, with no significant observed cross-talk effects.

  7. Influence of Structure and Surface Chemistry of Porous Carbon Electrodes on Supercapacitor Performance

    NASA Astrophysics Data System (ADS)

    Dyatkin, Boris

    Electrochemical double layer capacitors, which rely on electrosorption of ions in nanostructured carbon electrodes, can supplement or even replace traditional batteries in energy harvesting and storage applications. While supercapacitors offer > 10 kW/kg power densities, their ~5 Wh/kg energy densities are insufficient for many automotive and grid storage applications. Most prior efforts have focused on novel high-performing ionic liquid electrolytes and porous carbons with tunable pore diameters and high specific surface areas. However, existing research lacks fundamental understanding of the influence of surface heterogeneity and disorder, such as graphitic defects and functional groups, on key electrosorption properties at electrode-electrolyte interfaces. These interactions significantly impact charge accumulation densities, ion transport mechanisms, and electrolyte breakdown processes. Subsequently, they must be investigated to optimize ion screening, charge mobilities, and operating voltage windows of the devices. The research in this dissertation examined the influence of surface functional groups and structural ordering on capacitance, electrosorption dynamics, and electrochemical stability of external and internal surface of carbon electrodes. High-temperature vacuum annealing, air oxidation, hydrogenation, and amination were used to tune pore surface compositions and decouple key structural and chemical properties of carbide-derived carbons. The approach combined materials characterization by a variety of techniques, neutron scattering studies of ion dynamics, electrochemical testing, and MD simulations to investigate the fundamental intermolecular interactions and dynamics of ions electrosorption in different pore architectures and on planar graphene surfaces. Contrary to expected results and existing theories, defect removal via defunctionalization and graphitization decreased capacitance. Hydrogenated surfaces benefitted electrosorption, while oxygen

  8. Enzymatic deposition of Au nanoparticles on the designed electrode surface and its application in glucose detection.

    PubMed

    Zhang, Hongfang; Liu, Ruixiao; Sheng, Qinglin; Zheng, Jianbin

    2011-02-01

    This paper reported the enzymatic deposition of Au nanoparticles (AuNPs) on the designed 3-mercapto-propionic acid/glucose oxidase/chitosan (MPA/GOD/Chit) modified glassy carbon electrode and its application in glucose detection. Chit served as GOD immobilization matrix and interacted with MPA through electrostatic attraction. AuNPs, without nano-seeds presented on the electrode surface, was produced through the glucose oxidase catalyzed oxidation of glucose. The mechanism of production of AuNPs was confirmed to be that enzymatic reaction products H(2)O(2) in the solution reduce gold complex to AuNPs. The characterizations of the electrode modified after each assembly step was investigated by cyclic voltammetry and electrochemical impedance spectroscopy. Scanning electron microscopy showed the average particle size of the AuNPs is 40nm with a narrow particle size distribution. The content of AuNPs on the electrode surfaces was measured by differential pulse stripping voltammetry. The electrochemical signals on voltammogram showed a linear increase with the glucose concentration in the range of 0.010-0.12mM with a detection limit of 4μM. This provided a method to the determination of glucose. PMID:21115279

  9. Study of surface dielectric barrier discharge generated using liquid electrodes in different gases

    NASA Astrophysics Data System (ADS)

    Galmiz, O.; Pavlinak, D.; Zemanek, M.; Brablec, A.; Cernak, M.

    2016-02-01

    Surface dielectric barrier discharges with conductive water-solution electrodes were generated at atmospheric pressure air, nitrogen, oxygen, and argon. The discharges were studied by conventional and high-speed camera photography. Plasma rotational and vibrational temperatures and the electron number density were estimated using optical emission spectroscopy. Surprisingly, especially for oxygen, the discharge was found to generate visually diffuse strongly non-isothermal plasma. This observation indicates the interesting application potential of the discharge for surface plasma treatments of, i.e. the inner and outer surfaces of hollow dielectric bodies.

  10. Surface enhanced Raman scattering of new acridine based fluorophore adsorbed on silver electrode.

    PubMed

    Solovyeva, Elena V; Myund, Liubov A; Denisova, Anna S

    2015-10-01

    4,5-Bis(N,N-di(2-hydroxyethyl)iminomethyl)acridine (BHIA) is a new acridine based fluoroionophore and a highly-selective sensor for cadmium ion. The direct interaction of the aromatic nitrogen atom with a surface is impossible since there are bulky substituents in the 4,5-positions of the acridine fragment. Nevertheless BHIA molecule shows a reliable SERS spectrum while adsorbed on a silver electrode. The analysis of SERS spectra pH dependence reveals that BHIA species adsorbed on a surface can exist in both non-protonated and protonated forms. The adsorption of BHIA from alkaline solution is accompanied by carbonaceous species formation at the surface. The intensity of such "carbon bands" turned out to be related with the supporting electrolyte (KCl) concentration. Upon lowering the electrode potential the SERS spectra of BHIA do not undergo changes but the intensity of bands decreases. This indicates that the adsorption mechanism on the silver surface is realized via aromatic system of acridine fragment. In case of such an adsorption mechanism the chelate fragment of the BHIA molecule is capable of interaction with the solution components. Addition of Cd(2+) ions to a system containing BHIA adsorbed on a silver electrode in equilibrium with the solution leads to the formation of BHIA/Cd(2+) complex which desorption causes the loss of SERS signal. PMID:25956332

  11. Influence of surface oxidation on ion dynamics and capacitance in porous and nonporous carbon electrodes

    DOE PAGES

    Dyatkin, Boris; Zhang, Yu; Mamontov, Eugene; Kolesnikov, Alexander I.; Cheng, Yongqiang; Meyer, III, Harry M.; Cummings, Peter T.; Gogotsi, Yury G.

    2016-04-07

    Here, we investigate the influence of surface chemistry and ion confinement on capacitance and electrosorption dynamics of room-temperature ionic liquids (RTILs) in supercapacitors. Using air oxidation and vacuum annealing, we produced defunctionalized and oxygen-rich surfaces of carbide-derived carbons (CDCs) and graphene nanoplatelets (GNPs). While oxidized surfaces of porous CDCs improve capacitance and rate handling abilities of ions, defunctionalized nonporous GNPs improve charge storage densities on planar electrodes. Quasi-elastic neutron scattering (QENS) and inelastic neutron scattering (INS) probed the structure, dynamics, and orientation of RTIL ions confined in divergently functionalized pores. Oxidized, ionophilic surfaces draw ions closer to pore surfaces andmore » enhance potential-driven ion transport during electrosorption. Molecular dynamics (MD) simulations corroborated experimental data and demonstrated the significance of surface functional groups on ion orientations, accumulation densities, and capacitance.« less

  12. Oriented collagen as a potential cochlear implant electrode surface coating to achieve directed neurite outgrowth.

    PubMed

    Volkenstein, Stefan; Kirkwood, John E; Lai, Edwina; Dazert, Stefan; Fuller, Gerald G; Heller, Stefan

    2012-04-01

    In patients with severe to profound hearing loss, cochlear implants (CIs) are currently the only therapeutic option when the amplification with conventional hearing aids does no longer lead to a useful hearing experience. Despite its great success, there are patients in which benefit from these devices is rather limited. One reason may be a poor neuron-device interaction, where the electric fields generated by the electrode array excite a wide range of tonotopically organized spiral ganglion neurons at the cost of spatial resolution. Coating of CI electrodes to provide a welcoming environment combined with suitable surface chemistry (e.g. with neurotrophic factors) has been suggested to create a closer bioelectrical interface between the electrode array and the target tissue, which might lead to better spatial resolution, better frequency discrimination, and ultimately may improve speech perception in patients. Here we investigate the use of a collagen surface with a cholesteric banding structure, whose orientation can be systemically controlled as a guiding structure for neurite outgrowth. We demonstrate that spiral ganglion neurons survive on collagen-coated surfaces and display a directed neurite growth influenced by the direction of collagen fibril deposition. The majority of neurites grow parallel to the orientation direction of the collagen. We suggest collagen coating as a possible future option in CI technology to direct neurite outgrowth and improve hearing results for affected patients.

  13. Use of Surface Enhanced Blocking (SEB) Electrodes for Microbial Cell Lysis in Flow-Through Devices

    PubMed Central

    Talebpour, Abdossamad; Maaskant, Robert; Khine, Aye Aye; Alavie, Tino

    2014-01-01

    By simultaneously subjecting microbial cells to high amplitude pulsed electric fields and flash heating of the cell suspension fluid, effective release of intracellular contents was achieved. The synergistic effect of the applied electric field and elevated temperature on cell lysis in a flow-through device was demonstrated for Gram-negative and Gram-positive bacteria, and Mycobacterium species. The resulting lysate is suitable for downstream nucleic acid amplification and detection without requiring further preparation. The lysis chamber employs surface enhanced blocking electrodes which possess an etched micro-structured surface and a thin layer of dielectric metal oxide which provides a large effective area and blocks transmission of electrical current. The surface enhanced blocking electrodes enable simultaneous suppression of the rapid onset of electric field screening in the bulk of the cell suspension medium and avoidance of undesired electrochemical processes at the electrode-electrolyte interface. In addition the blocking layer ensures the robustness of the cell lysis device in applications involving prolonged flow-through processing of the microbial cells. PMID:25033080

  14. Silver corrosion and sulfur detection using a quartz crystal microbalance with silver electrode surfaces

    SciTech Connect

    Zabarnick, S.; Zelesnik, P.; Whitacre, S.D.

    1996-08-01

    A quartz crystal microbalance (QCM) with silver electrodes is used for detection of sulfur and measurement of silver corrosion by sulfur in jet fuels. It is found that the device responds very sensitively to elemental sulfur by reaction at the silver surface, resulting in the formation of surface silver sulfide. It is also expected that the device will respond to hydrogen sulfide. The response of the QCM is found to depend on the fuel matrix. The presence of oxygen inhibits the surface reaction, resulting in a lower mass accumulation. It is also found that the sulfur compounds which produce a response in this test are not players in the formation of autoxidative surface deposition. It is shown that the QCM response (surface mass per unit time) is proportional to the concentration of elemental sulfur present in the fuel.

  15. Engineering nanostructures and surface chemistry of efficient lithium ion intercalation electrodes

    NASA Astrophysics Data System (ADS)

    Liu, Dawei

    Lithium ion batteries have been one of the major power supplies for small electronic devices since last century. However, with the rapid advancement of electronics and the increasing demand for clean sustainable energy, newer lithium ion batteries with higher energy density, higher power density, and better cyclic stability are needed. In addition, newer generation of lithium ion batteries must meet the requirements of low and easy fabrication cost and free of toxic materials. Nanostructured electrodes are seemingly the most promising candidate for future lithium ion batteries. In our experiments, mesoporous MnO2 nanowall arrays were fabricated through water electrolysis induced precipitation. Thus-fabricated arrays delivered capacities upto 256 mAhg-1, nearly double the theoretical value of 140 mAhg -1 from bulk MnO2. Modification of nanostructured electrode surface chemistry was found to contribute to lithium ion intercalation rate capability. Anodized TiO2 nanotube arrays after annealing in CO at 400°C, with TiC and Ti3+ species present on the surface, exhibited a much enhanced rate capability as compared with arrays without noticeable surface defects. Manipulating the crystallinity of electrodes could be another method to improve the intercalation capability. V2O5 xerogel films with less crystallized structure exhibited higher intercalation capacity and better cyclic stability than well crystallized counterpart. Materials possessing nanostructures, surface and bulk defects and in poor crystallinity or amorphous state are all away from equilibrium state. The electrodes away from equilibrium state have demonstrated favorable lithium ion intercalation properties. The contribution of non-equilibrium state lies in three aspects: (1) enhancing the storage capacity by shifting the phase transition boundary; (2) improving the rate capability by introducing fast mass and charge transport path; and (3) allowing longer cyclic stability by permitting more freedom for

  16. Prediction of the thermal sensitivity of surface acoustic waves excited under a periodic grating of electrodes.

    PubMed

    Pastureaud, Thomas; Lardat, Raphael; Chamaly, Stéphane; Pénavaire, Louis; Ballandras, Sylvain

    2005-08-01

    The prediction of the temperature sensitivity of surface acoustic wave (SAW) devices still requires improvement because the nature of the implemented surface modes and the devices' complexity strongly change from the early basic Rayleigh-wave-based devices. To address this problem, a theoretical analysis and a numerical tool have been developed to predict the thermal dispersion of general electro-acoustic devices. The proposed model accounts for the electrode contribution to the frequency-temperature law. The computed thermal sensitivities are compared to experimental results for different kinds of substrates and waves.

  17. Studying the glial cell response to biomaterials and surface topography for improving the neural electrode interface

    NASA Astrophysics Data System (ADS)

    Ereifej, Evon S.

    Neural electrode devices hold great promise to help people with the restoration of lost functions, however, research is lacking in the biomaterial design of a stable, long-term device. Current devices lack long term functionality, most have been found unable to record neural activity within weeks after implantation due to the development of glial scar tissue (Polikov et al., 2006; Zhong and Bellamkonda, 2008). The long-term effect of chronically implanted electrodes is the formation of a glial scar made up of reactive astrocytes and the matrix proteins they generate (Polikov et al., 2005; Seil and Webster, 2008). Scarring is initiated when a device is inserted into brain tissue and is associated with an inflammatory response. Activated astrocytes are hypertrophic, hyperplastic, have an upregulation of intermediate filaments GFAP and vimentin expression, and filament formation (Buffo et al., 2010; Gervasi et al., 2008). Current approaches towards inhibiting the initiation of glial scarring range from altering the geometry, roughness, size, shape and materials of the device (Grill et al., 2009; Kotov et al., 2009; Kotzar et al., 2002; Szarowski et al., 2003). Literature has shown that surface topography modifications can alter cell alignment, adhesion, proliferation, migration, and gene expression (Agnew et al., 1983; Cogan et al., 2005; Cogan et al., 2006; Merrill et al., 2005). Thus, the goals of the presented work are to study the cellular response to biomaterials used in neural electrode fabrication and assess surface topography effects on minimizing astrogliosis. Initially, to examine astrocyte response to various materials used in neural electrode fabrication, astrocytes were cultured on platinum, silicon, PMMA, and SU-8 surfaces, with polystyrene as the control surface. Cell proliferation, viability, morphology and gene expression was measured for seven days in vitro. Results determined the cellular characteristics, reactions and growth rates of astrocytes

  18. Conducting elastomer surface texturing: a path to electrode spotting. Application to the biochip production.

    PubMed

    Marquette, Christophe A; Blum, Loïc J

    2004-09-15

    A new active support for electro-chemiluminescent biochip preparation has been developed. This material was based on an original material composed of graphite modified polydimethyl siloxane (PDMS). The addressed inclusion of Sepharose beads at the surface of this elastomeric electrode generated interesting local high specific surface. The electrode was characterised by electrochemical (cyclic voltametry, chronoamperomatry) and imaging (scanning electron microscopy (SEM)) methods, and a surface area increase factor of 50 was found, linked to the texturing of the surface generated by the presence of the Sepharose beads. The consequence of this increase was shown to be a jump of the local electrochemical activity which induced a well defined and localised electro-chemiluminescent signal. The new material was used to design biochips based on the electro-chemiluminescent reaction of luminol with enzymatically produced hydrogen peroxide. Thus, when using beads bearing bio-molecules such nucleic acid or human IgG, in conjunction with glucose oxidas-labelled DNA or antibody, sensitive biochips could be obtained with detection limits of 10(11) and 10(10) molecules, respectively. Multi-parameter enzyme-based biochips could also be achieved by locally adsorbing, at the PDMS-graphite surface, either glucose oxidase, lactate oxidase or choline oxidase. Detection limits of 10 microM for lactate and choline and 20 microM for glucose were found, with detection ranging over two decades at least.

  19. Transitions from near-surface to interior redox upon lithiation in conversion electrode materials.

    PubMed

    He, Kai; Xin, Huolin L; Zhao, Kejie; Yu, Xiqian; Nordlund, Dennis; Weng, Tsu-Chien; Li, Jing; Jiang, Yi; Cadigan, Christopher A; Richards, Ryan M; Doeff, Marca M; Yang, Xiao-Qing; Stach, Eric A; Li, Ju; Lin, Feng; Su, Dong

    2015-02-11

    Nanoparticle electrodes in lithium-ion batteries have both near-surface and interior contributions to their redox capacity, each with distinct rate capabilities. Using combined electron microscopy, synchrotron X-ray methods and ab initio calculations, we have investigated the lithiation pathways that occur in NiO electrodes. We find that the near-surface electroactive (Ni(2+) → Ni(0)) sites saturated very quickly, and then encounter unexpected difficulty in propagating the phase transition into the electrode (referred to as a "shrinking-core" mode). However, the interior capacity for Ni(2+) → Ni(0) can be accessed efficiently following the nucleation of lithiation "fingers" that propagate into the sample bulk, but only after a certain incubation time. Our microstructural observations of the transition from a slow shrinking-core mode to a faster lithiation finger mode corroborate with synchrotron characterization of large-format batteries and can be rationalized by stress effects on transport at high-rate discharge. The finite incubation time of the lithiation fingers sets the intrinsic limitation for the rate capability (and thus the power) of NiO for electrochemical energy storage devices. The present work unravels the link between the nanoscale reaction pathways and the C-rate-dependent capacity loss and provides guidance for the further design of battery materials that favors high C-rate charging.

  20. Transitions from near-surface to interior redox upon lithiation in conversion electrode materials

    SciTech Connect

    He, Kai; Xin, Huolin L.; Zhao, Kejie; Yu, Xiqian; Norlund, Dennis; Weng, Tsu-Chien; Li, Jing; Jiang, Yi; Cadigan, Christopher A.; Richards, Ryan M.; Doeff, Marca M.; Yang, Xiao-Qing; Stach, Eric A.; Li, Ju; Lin, Feng; Su, Dong

    2015-01-29

    Nanoparticle electrodes in lithium-ion batteries have both near-surface and interior contributions to their redox capacity, each with distinct rate capabilities. Using combined electron microscopy, synchrotron X-ray methods and ab initio calculations, we have investigated the lithiation pathways that occur in NiO electrodes. We find that the near-surface electroactive (Ni²⁺→Ni⁰) sites saturated very quickly, and then encounter unexpected difficulty in propagating the phase transition into the electrode (referred to as a “shrinking-core” mode). However, the interior capacity for Ni²⁺→Ni⁰ can be accessed efficiently following the nucleation of lithiation “fingers” which propagate into the sample bulk, but only after a certain incubation time. Our microstructural observations of the transition from a slow shrinking-core mode to a faster lithiation finger mode corroborate with synchrotron characterization of large-format batteries, and can be rationalized by stress effects on transport at high-rate discharge. The finite incubation time of the lithiation fingers sets the intrinsic limitation for the rate capability (and thus the power) of NiO for electrochemical energy storage devices. The present work unravels the link between the nanoscale reaction pathways and the C-rate-dependent capacity loss, and provides guidance for the further design of battery materials that favors high C-rate charging.

  1. Transitions from near-surface to interior redox upon lithiation in conversion electrode materials

    DOE PAGES

    He, Kai; Xin, Huolin L.; Zhao, Kejie; Yu, Xiqian; Norlund, Dennis; Weng, Tsu-Chien; Li, Jing; Jiang, Yi; Cadigan, Christopher A.; Richards, Ryan M.; et al

    2015-01-29

    Nanoparticle electrodes in lithium-ion batteries have both near-surface and interior contributions to their redox capacity, each with distinct rate capabilities. Using combined electron microscopy, synchrotron X-ray methods and ab initio calculations, we have investigated the lithiation pathways that occur in NiO electrodes. We find that the near-surface electroactive (Ni²⁺→Ni⁰) sites saturated very quickly, and then encounter unexpected difficulty in propagating the phase transition into the electrode (referred to as a “shrinking-core” mode). However, the interior capacity for Ni²⁺→Ni⁰ can be accessed efficiently following the nucleation of lithiation “fingers” which propagate into the sample bulk, but only after a certain incubationmore » time. Our microstructural observations of the transition from a slow shrinking-core mode to a faster lithiation finger mode corroborate with synchrotron characterization of large-format batteries, and can be rationalized by stress effects on transport at high-rate discharge. The finite incubation time of the lithiation fingers sets the intrinsic limitation for the rate capability (and thus the power) of NiO for electrochemical energy storage devices. The present work unravels the link between the nanoscale reaction pathways and the C-rate-dependent capacity loss, and provides guidance for the further design of battery materials that favors high C-rate charging.« less

  2. Voltammetric and impedance behaviours of surface-treated nano-crystalline diamond film electrodes

    SciTech Connect

    Liu, F. B.; Jing, B.; Cui, Y.; Di, J. J.; Qu, M.

    2015-04-15

    The electrochemical performances of hydrogen- and oxygen-terminated nano-crystalline diamond film electrodes were investigated by cyclic voltammetry and AC impedance spectroscopy. In addition, the surface morphologies, phase structures, and chemical states of the two diamond films were analysed by scanning probe microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy, respectively. The results indicated that the potential window is narrower for the hydrogen-terminated nano-crystalline diamond film than for the oxygen-terminated one. The diamond film resistance and capacitance of oxygen-terminated diamond film are much larger than those of the hydrogen-terminated diamond film, and the polarization resistances and double-layer capacitance corresponding to oxygen-terminated diamond film are both one order of magnitude larger than those corresponding to the hydrogen-terminated diamond film. The electrochemical behaviours of the two diamond film electrodes are discussed.

  3. Investigation of a Solution-Processable, Nonspecific Surface Modifier for Low Cost, High Work Function Electrodes.

    PubMed

    Hinckley, Allison C; Wang, Congcong; Pfattner, Raphael; Kong, Desheng; Zhou, Yan; Ecker, Ben; Gao, Yongli; Bao, Zhenan

    2016-08-01

    We demonstrate the ability of the highly fluorinated, chemically inert copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) to significantly increase the work function of a variety of common electrode materials. The work function change is hypothesized to occur via physisorption of the polymer layer and formation of a surface dipole at the polymer/conductor interface. When incorporated into organic solar cells, an interlayer of PVDF-HFP at an Ag anode increases the open circuit voltage by 0.4 eV and improves device power conversion efficiency by approximately an order of magnitude relative to Ag alone. Solution-processable in air, PVDF-HFP thin films provide one possible route toward achieving low cost, nonreactive, high work function electrodes. PMID:27428045

  4. Surface modification and electrochemical properties of activated carbons for supercapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Yang, Dan; Qiu, Wenmei; Xu, Jingcai; Han, Yanbing; Jin, Hongxiao; Jin, Dingfeng; Peng, Xiaoling; Hong, Bo; Li, Ji; Ge, Hongliang; Wang, Xinqing

    2015-12-01

    Modifications with different acids (HNO3, H2SO4, HCl and HF, respectively) were introduced to treat the activated carbons (ACs) surface. The microstructures and surface chemical properties were discussed by X-ray diffraction (XRD), thermogravimetric analysis (TGA), ASAP, Raman spectra and Fourier transform infrared (FTIR) spectra. The ACs electrode-based supercapacitors were assembled with 6 mol ṡ L-1 KOH electrolyte. The electrochemical properties were studied by galvanostatic charge-discharge and cyclic voltammetry. The results indicated that although the BET surface area of modified ACs decreased, the functional groups were introduced and the ash contents were reduced on the surface of ACs, receiving larger specific capacitance to initial AC. The specific capacitance of ACs modified with HCl, H2SO4, HF and HNO3 increased by 31.4%, 23%, 21% and 11.6%, respectively.

  5. Surface modification of battery electrodes via electroless deposition with improved performance for Na-ion batteries.

    PubMed

    Lahiri, Abhishek; Olschewski, Mark; Gustus, René; Borisenko, Natalia; Endres, Frank

    2016-06-01

    Sodium-ion batteries (SIBs) are emerging as potential stationary energy storage devices due to the abundance and low cost of sodium. A simple and energy efficient strategy to develop electrodes for SIBs with a high charge/discharge rate is highly desirable. Here we demonstrate that by surface modification of Ge, using electroless deposition in SbCl3/ionic liquids, the stability and performance of the anode can be improved. This is due to the formation of GexSb1-x at the surface leading to better diffusion of Na, and the formation of a stable twin organic and inorganic SEI which protects the electrode. By judicious control of the surface modification, an improvement in the capacity to between 50% and 300% has been achieved at high current densities (0.83-8.4 A g(-1)) in an ionic liquid electrolyte NaFSI-[Py1,4]FSI. The results clearly demonstrate that an electroless deposition based surface modification strategy in ionic liquids offers exciting opportunities in developing superior energy storage devices.

  6. Crystallographic orientation and electrode nature are key factors for electric current generation by Geobacter sulfurreducens.

    PubMed

    Maestro, Beatriz; Ortiz, Juan M; Schrott, Germán; Busalmen, Juan P; Climent, Víctor; Feliu, Juan M

    2014-08-01

    We have investigated the influence of electrode material and crystallographic structure on electron transfer and biofilm formation of Geobacter sulfurreducens. Single-crystal gold-Au(110), Au(111), Au(210)-and platinum-Pt(100), Pt(110), Pt(111), Pt(210)-electrodes were tested and compared to graphite rods. G. sulfurreducens electrochemically interacts with all these materials with different attachment kinetics and final current production, although redox species involved in the electron transfer to the anode are virtually the same in all cases. Initial bacterial colonization was fastest on graphite up to the monolayer level, whereas gold electrodes led to higher final current densities. Crystal geometry was shown to have an important influence, with Au(210) sustaining a current density of up to 1442±101μAcm(-2) at the steady state, over Au(111) with 961±94μAcm(-2) and Au(110) with 944±89μAcm(-2). On the other hand, the platinum electrodes displayed the lowest performances, including Pt(210). Our results indicate that both crystal geometry and electrode material are key parameters for the efficient interaction of bacteria with the substrate and should be considered for the design of novel materials and microbial devices to optimize energy production.

  7. Crystallographic orientation and electrode nature are key factors for electric current generation by Geobacter sulfurreducens.

    PubMed

    Maestro, Beatriz; Ortiz, Juan M; Schrott, Germán; Busalmen, Juan P; Climent, Víctor; Feliu, Juan M

    2014-08-01

    We have investigated the influence of electrode material and crystallographic structure on electron transfer and biofilm formation of Geobacter sulfurreducens. Single-crystal gold-Au(110), Au(111), Au(210)-and platinum-Pt(100), Pt(110), Pt(111), Pt(210)-electrodes were tested and compared to graphite rods. G. sulfurreducens electrochemically interacts with all these materials with different attachment kinetics and final current production, although redox species involved in the electron transfer to the anode are virtually the same in all cases. Initial bacterial colonization was fastest on graphite up to the monolayer level, whereas gold electrodes led to higher final current densities. Crystal geometry was shown to have an important influence, with Au(210) sustaining a current density of up to 1442±101μAcm(-2) at the steady state, over Au(111) with 961±94μAcm(-2) and Au(110) with 944±89μAcm(-2). On the other hand, the platinum electrodes displayed the lowest performances, including Pt(210). Our results indicate that both crystal geometry and electrode material are key parameters for the efficient interaction of bacteria with the substrate and should be considered for the design of novel materials and microbial devices to optimize energy production. PMID:24642203

  8. Simultaneous measurements of wire electrode surface contamination and corona discharge characteristics in an air-cleaning electrostatic precipitator

    SciTech Connect

    Kanazawa, Seiji; Ohkubo, Toshikazu; Nomoto, Yukiharu; Adachi, Takayoshi; Chang, J.S.

    1997-01-01

    Contamination of the corona wire in a wire-to-plate type air-cleaning electrostatic precipitator is studied experimentally. In order to enhance the contamination of wire, air containing dusts is directly supplied to a part of the wire electrode. Spores of Lycopodium and cigarette smoke particles are used as test dusts. Simultaneous measurements of wire electrode optical images and corona discharge modes are carried out during contamination processes. Results show that corona discharge modes and optical emission from the wire electrode change with time due to the surface contamination. In the case of cigarette smoke, after a time elapsed, streamer coronas appear due to the buildup of smoke particles on the wire surface. After the first streamer generation, the corona current fluctuates with time because the formation and diminution of the projections occur alternately at the different parts on the wire electrode surface.

  9. Using electrochemistry - total internal refection imaging ellipsometry to monitor biochemical oxygen demand on the surface tethered polyelectrolyte modified electrode

    NASA Astrophysics Data System (ADS)

    Liu, Wei; Li, Meng; Lv, Bei'er; Chen, YanYan; Ma, Hongwei; Jin, Gang

    2015-03-01

    Our previous work has proposed an electrochemistry - total internal reflection imaging ellipsometry (EC-TIRIE) technique to observe the dissolved oxygen (DO) reduction on Clark electrode since high interface sensitivity makes TIRIE a useful tool to study redox reactions on the electrode surface. To amplify the optical signal noise ratio (OSNR), a surface tethered weak polyelectrolyte, carboxylated poly(oligo(ethylene glycol) methacrylate-random- 2-hydroxyethylmethacrylate) (abbreviated as carboxylated poly(OEGMA-r-HEMA)), has been introduced on the electrode surface. Since Clark electrode is widely used in biochemical oxygen demand (BOD) detection, we use this technique to measure BOD in the sample. The dynamic range of the system is from 0 ˜ 25 mg/L. Two samples have been measured. Compared with the conventional method, the deviation of both optical and electrical signals are less than 10%.

  10. Effects of electrode surface modification with chlorotoxin on patterning single glioma cells.

    PubMed

    Asphahani, Fareid; Zheng, Xiaohao; Veiseh, Omid; Thein, Myo; Xu, Jian; Ohuchi, Fumio; Zhang, Miqin

    2011-05-21

    A microchip patterned with arrays of single cancer cells can be an effective platform for the study of tumor biology, medical diagnostics, and drug screening. However, patterning and retaining viable single cancer cells on defined sites of the microarray can be challenging. In this study we used a tumor cell-specific peptide, chlorotoxin (CTX), to mediate glioma cell adhesion on arrays of gold microelectrodes and investigated the effects of three surface modification schemes for conjugation of CTX to the microelectrodes on single cell patterning, which include physical adsorption, covalent bonding mediated by N-hydroxysuccinimide (NHS), and covalent bonding via crosslinking succinimidyl iodoacetate and Traut's (SIA-Traut) reagents. The CTX immobilization to microelectrodes was confirmed by high-resolution X-ray photoelectron spectroscopy. Physically adsorbed CTX showed better support for cell adhesion and is more effective in confining adhered cells on the electrodes than covalently-bound CTX. Furthermore, cell adhesion and spreading on microelectrodes were quantified in real-time by impedance measurements, which revealed an impedance signal from physically adsorbed CTX electrodes four times greater than the signal from covalently-bound CTX electrodes.

  11. Studying the glial cell response to biomaterials and surface topography for improving the neural electrode interface

    NASA Astrophysics Data System (ADS)

    Ereifej, Evon S.

    Neural electrode devices hold great promise to help people with the restoration of lost functions, however, research is lacking in the biomaterial design of a stable, long-term device. Current devices lack long term functionality, most have been found unable to record neural activity within weeks after implantation due to the development of glial scar tissue (Polikov et al., 2006; Zhong and Bellamkonda, 2008). The long-term effect of chronically implanted electrodes is the formation of a glial scar made up of reactive astrocytes and the matrix proteins they generate (Polikov et al., 2005; Seil and Webster, 2008). Scarring is initiated when a device is inserted into brain tissue and is associated with an inflammatory response. Activated astrocytes are hypertrophic, hyperplastic, have an upregulation of intermediate filaments GFAP and vimentin expression, and filament formation (Buffo et al., 2010; Gervasi et al., 2008). Current approaches towards inhibiting the initiation of glial scarring range from altering the geometry, roughness, size, shape and materials of the device (Grill et al., 2009; Kotov et al., 2009; Kotzar et al., 2002; Szarowski et al., 2003). Literature has shown that surface topography modifications can alter cell alignment, adhesion, proliferation, migration, and gene expression (Agnew et al., 1983; Cogan et al., 2005; Cogan et al., 2006; Merrill et al., 2005). Thus, the goals of the presented work are to study the cellular response to biomaterials used in neural electrode fabrication and assess surface topography effects on minimizing astrogliosis. Initially, to examine astrocyte response to various materials used in neural electrode fabrication, astrocytes were cultured on platinum, silicon, PMMA, and SU-8 surfaces, with polystyrene as the control surface. Cell proliferation, viability, morphology and gene expression was measured for seven days in vitro. Results determined the cellular characteristics, reactions and growth rates of astrocytes

  12. Determination of photoelectrochemical water oxidation intermediates on haematite electrode surfaces using operando infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Zandi, Omid; Hamann, Thomas W.

    2016-08-01

    Semiconductor electrodes capable of using solar photons to drive water-splitting reactions, such as haematite (α-Fe2O3), have been the subject of tremendous interest over recent decades. The surface has been found to play a significant role in determining the efficiency of water oxidation with haematite; however, previous works have only allowed hypotheses to be formulated regarding the identity of relevant surface species. Here we investigate the water-oxidation reaction on haematite using infrared spectroscopy under photoelectrochemical (PEC) water-oxidation conditions. A potential- and light-dependent absorption peak at 898 cm‑1 is assigned to a FeIV=O group, which is an intermediate in the PEC water-oxidation reaction. These results provide direct evidence of high-valent iron–oxo intermediates as the product of the first hole-transfer reaction on the haematite surface and represent an important step in establishing the mechanism of PEC water oxidation on semiconductor electrodes.

  13. Determination of photoelectrochemical water oxidation intermediates on haematite electrode surfaces using operando infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Zandi, Omid; Hamann, Thomas W.

    2016-08-01

    Semiconductor electrodes capable of using solar photons to drive water-splitting reactions, such as haematite (α-Fe2O3), have been the subject of tremendous interest over recent decades. The surface has been found to play a significant role in determining the efficiency of water oxidation with haematite; however, previous works have only allowed hypotheses to be formulated regarding the identity of relevant surface species. Here we investigate the water-oxidation reaction on haematite using infrared spectroscopy under photoelectrochemical (PEC) water-oxidation conditions. A potential- and light-dependent absorption peak at 898 cm-1 is assigned to a FeIV=O group, which is an intermediate in the PEC water-oxidation reaction. These results provide direct evidence of high-valent iron-oxo intermediates as the product of the first hole-transfer reaction on the haematite surface and represent an important step in establishing the mechanism of PEC water oxidation on semiconductor electrodes.

  14. Magnetic cooling at a single molecule level: a spectroscopic investigation of isolated molecules on a surface.

    PubMed

    Corradini, Valdis; Ghirri, Alberto; Candini, Andrea; Biagi, Roberto; del Pennino, Umberto; Dotti, Gianluca; Otero, Edwige; Choueikani, Fadi; Blagg, Robin J; McInnes, Eric J L; Affronte, Marco

    2013-05-28

    A sub-monolayer distribution of isolated molecular Fe14 (bta)6 nanomagnets is deposited intact on a Au(111) surface and investigated by X-ray magnetic circular dichroism spectroscopy. The entropy variation with respect to the applied magnetic field is extracted from the magnetization curves and evidences high magnetocaloric values at the single molecule level.

  15. Impact of Surface Chemistry on Nanoparticle-Electrode Interactions in the Electrochemical Detection of Nanoparticle Collisions.

    PubMed

    Chen, Chang-Hui; Ravenhill, Emma R; Momotenko, Dmitry; Kim, Yang-Rae; Lai, Stanley C S; Unwin, Patrick R

    2015-11-01

    The electrochemical detection of a single nanoparticle (NP) at a support electrode can provide key information on surface chemistry and fundamental electron transfer (ET) properties at the nanoscale. This study employs scanning electrochemical cell microscopy (SECCM) as a fluidic device to both deliver individual citrate-capped gold nanoparticles (AuNPs) and study the interactions between them and a range of alkanethiol-modified Au electrodes with different terminal groups, namely, -COOH, -OH, and -CH3. Single NP collisions were detected through the AuNP-mediated ET reaction of Fe(CN)6(4-/3-) in aqueous solution. The collision frequency, residence time, and current-time characteristics of AuNPs are greatly affected by the terminal groups of the alkanethiol. Methods to determine these parameters, including the effect of the instrument response function, and derive ET kinetics are outlined. To further understand the interactions of AuNPs with these surfaces, atomic force microscopy (AFM) force measurements were performed using citrate-modified Au-coated AFM tips and the same alkanethiol-modified Au substrates in aqueous solution at the same potential bias as for the AuNP collision experiments. Force curves on OH-terminated surfaces showed no repulsion and negligible adhesion force. In contrast, a clear repulsion (on approach) was seen for COOH-terminated surface and adhesion forces (on retract) were observed for both COOH- and CH3-terminated surfaces. These interactions help to explain the residence times and collision frequencies in AuNP collisions. More generally, as the interfacial properties probed by AFM appear to be amplified in NP collision experiments, and new features also become evident, it is suggested that such experiments provide a new means of probing surface chemistry at the nanoscale.

  16. Macrokinetics of H/sub 2/O/sub 2/ electroreduction in a capillary gap at electrodes with rough surface

    SciTech Connect

    Koshel', N.D.; Cherednichenko, A.S.

    1984-08-01

    It is expected that the structure of the electrode surface which regulates mass transport conditions will have an important effect on the ratio between the rates of H/sub 2/O/sub 2/ electroreduction and heterogeneous decomposition. To elucidate the mechanisms of this surface effect the authors investigated nickel foil electrodes with corrugated triangular profile (with a height of 350 micrometers) which were activated with silver, platinum, and palladium. Three types of electrode were used: with a smooth surface (Ag, Pd); with a microscopically rough surface obtained either by straightforward deposition of highly disperse catalyst black (Pt) or by depositing the catalyst (Ag) onto a precoat of inactive nickel black, and with a macroscopically rough surface obtained by the electrolysis of carbonyl nickel suspension in a nickel plating bath and subsequent activation (Ag).

  17. Diphenyl viologen on an HOPG electrode surface: less sharp redox wave than dibenzyl viologen.

    PubMed

    Higashi, Tomohiro; Sagara, Takamasa

    2013-09-10

    Redox behavior of diphenyl viologen (dPhV) on a basal plane of a highly oriented pyrolytic graphite (HOPG) electrode was described using the results of voltammetric and electroreflectance measurements. Its characteristics were compared to those of dibenzyl viologen (dBV), which undergoes the first-order faradaic phase transition. Unlike dBV, dPhV-dication (dPhV(2+)) was found to take a strongly adsorbed state on an HOPG surface. This is due to much stronger π-π interaction between phenyl rings of dPhV(2+) and HOPG surface than between benzyl groups of dBV(2+) and the surface. The participation of this strongly adsorbed dPhV(2+) in the redox process can be avoided by (1) a shorter than ∼3 min time period elapsing from touching a freshly cleaved HOPG surface to dPhV solution until the start of potential scan, (2) complete equilibration at the electrode potentials at which superficial dPhV molecules are fully reduced, or (3) multiple cyclic potential scanning to repeat oxidation-reduction of adsorbed species. Even in such conditions, although voltammograms of thin-layer electrochemistry for the surface-confined dPhV(•+)/dPhV(2+) couple are obtained with peak widths being as narrow as those of dBV, it is not the first-order phase transition. The participation of strongly adsorbed dPhV(2+) molecules results in another new voltammetric feature with a broader peak. The film formed by strongly adsorbed dPhV(2+) was hydrophilic, whereas dBV(2+) does not form such a film but only a gas-like layer. Measurements using X-ray photoelectron spectroscopy confirmed that the film consists of dPhV(2+) with coexistent water. These results reveal a typical case that delicate interaction balance among V(2+), V(•+), and electrode surface determines whether the two-dimensional first-order transition takes place or not.

  18. Surface enhanced raman spectroscopy of pyridine on Ag electrodes. Surface complex formation

    NASA Astrophysics Data System (ADS)

    Pettinger, B.; Wtzel, H.

    1981-03-01

    Experimental evidence is given for surface complexes consisting of metal-adatom, pyridine and halide ions with which the surface enhanced Raman process can occur. A large part of the enhanced continuum turns out to result from a super-position of numerous extremely weak SER lines attributed to these complexes.

  19. Fabric-Based Wearable Dry Electrodes for Body Surface Biopotential Recording.

    PubMed

    Yokus, Murat A; Jur, Jesse S

    2016-02-01

    A flexible and conformable dry electrode design on nonwoven fabrics is examined as a sensing platform for biopotential measurements. Due to limitations of commercial wet electrodes (e.g., shelf life, skin irritation), dry electrodes are investigated as the potential candidates for long-term monitoring of ECG signals. Multilayered dry electrodes are fabricated by screen printing of Ag/AgCl conductive inks on flexible nonwoven fabrics. This study focuses on the investigation of skin-electrode interface, form factor design, electrode body placement of printed dry electrodes for a wearable sensing platform. ECG signals obtained with dry and wet electrodes are comparatively studied as a function of body posture and movement. Experimental results show that skin-electrode impedance is influenced by printed electrode area, skin-electrode interface material, and applied pressure. The printed electrode yields comparable ECG signals to wet electrodes, and the QRS peak amplitude of ECG signal is dependent on printed electrode area and electrode on body spacing. Overall, fabric-based printed dry electrodes present an inexpensive health monitoring platform solution for mobile wearable electronics applications by fulfilling user comfort and wearability.

  20. Magnetohydrodynamic electrode

    DOEpatents

    Boquist, Carl W.; Marchant, David D.

    1978-01-01

    A ceramic-metal composite suitable for use in a high-temperature environment consists of a refractory ceramic matrix containing 10 to 50 volume percent of a continuous high-temperature metal reinforcement. In a specific application of the composite, as an electrode in a magnetohydrodynamic generator, the one surface of the electrode which contacts the MHD fluid may have a layer of varying thickness of nonreinforced refractory ceramic for electrode temperature control. The side walls of the electrode may be coated with a refractory ceramic insulator. Also described is an electrode-insulator system for a MHD channel.

  1. Theoretical approach for optical response in electrochemical systems: Application to electrode potential dependence of surface-enhanced Raman scattering

    SciTech Connect

    Iida, Kenji; Noda, Masashi; Nobusada, Katsuyuki

    2014-09-28

    We propose a theoretical approach for optical response in electrochemical systems. The fundamental equation to be solved is based on a time-dependent density functional theory in real-time and real-space in combination with its finite temperature formula treating an electrode potential. Solvation effects are evaluated by a dielectric continuum theory. The approach allows us to treat optical response in electrochemical systems at the atomistic level of theory. We have applied the method to surface-enhanced Raman scattering (SERS) of 4-mercaptopyridine on an Ag electrode surface. It is shown that the SERS intensity has a peak as a function of the electrode potential. Furthermore, the real-space computational approach facilitates visualization of variation of the SERS intensity depending on an electrode potential.

  2. Experimental Study on Surface Dielectric Barrier Discharge Plasma Actuator with Different Encapsulated Electrode Widths for Airflow Control at Atmospheric Pressure

    NASA Astrophysics Data System (ADS)

    Qi, Xiaohua; Yang, Liang; Yan, Huijie; Jin, Ying; Hua, Yue; Ren, Chunsheng

    2016-10-01

    The surface dielectric barrier discharge (SDBD) plasma actuator has shown great promise as an aerodynamic flow control device. In this paper, the encapsulated electrode width of a SDBD actuator is changed to study the airflow acceleration behavior. The effects of encapsulated electrode width on the actuator performance are experimentally investigated by measuring the dielectric layer surface potential, time-averaged ionic wind velocity and thrust force. Experimental results show that the airflow velocity and thrust force increase with the encapsulated electrode width. The results can be attributed to the distinct plasma distribution at different encapsulated electrode widths. supported by National Natural Science Foundation of China (No. 11175037), National Natural Science Foundation for Young Scientists of China (No. 11305017) and Special Fund for Theoretical Physics (No. 11247239)

  3. Deposition of wear-resistant steel surfaces by the plasma rotating electrode coating process

    NASA Astrophysics Data System (ADS)

    Kim, Michael Robert

    A high-deposition rate thermal spray method was investigated for the purpose of coating aluminum cylinder bores with a wear resistant surface. This method, the plasma rotating electrode coating system (PROTEC) utilized transferred-arc melting of a rapidly rotating consumable electrode to create a droplet stream via centrifugal atomization. A cylindrical substrate was placed around the rotating rod, in the flight path of the droplets, to deposit a coating onto the internal surface of the cylinder. Selected coatings of 1045 steel deposited by the PROTEC coating method exhibited lower wear loss in lubricated sliding than wire-arc sprayed carbon steel coatings and gray cast iron. Splat cohesion was shown to be a significant factor in the wear resistance of PROTEC coatings. The relationship between deposition enthalpy and cooling rate of the coating was found to have the greatest effect on coating microstructure, and the coating cohesion. The most rapidly solidified coatings showed inferior splat cohesion in comparison to coatings that cooled more slowly. The increase in splat cohesion with decreased cooling rate was accompanied by the formation of a directionally oriented coating microstructure, likely formed during cellular solidification of the coating. A model describing the thermal state of the deposition process was used to predict the deposition conditions that would result in a cellular structure, and the level of splat cohesion required to produce a wear resistant coating.

  4. Electrochemical study of functionalization on the surface of a chitin/platinum-modified glassy carbon paste electrode.

    PubMed

    Sugawara, Kazuharu; Yugami, Asako; Terui, Norifumi; Kuramitz, Hideki

    2009-11-01

    To functionalize chitin surfaces using proteins, we developed a glucose oxidase (GOD)-chitin/platinum-modified glassy carbon paste electrode (GCPE) as a model. In a weakly acidic solution, negatively charged GOD were immobilized by the protonated acetylamide groups on chitin. When the electrode was immersed in a solution containing GOD, the enzyme was readily immobilized due to the electrostatic interaction. In addition, measurements were performed using electrodes made with powders of different sizes because sensor performance depends on the particle sizes of glassy carbon powder. PMID:19907096

  5. Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. [Coal pyrite electrodes

    SciTech Connect

    Doyle, F.M.

    1992-01-01

    The objective of this research is to develop a mechanistic understanding of the oxidation of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with those surface properties that influence the behavior in physical cleaning processes. The results will provide fundamental insight into oxidation, in terms of the bulk and surface chemistry, the microstructure, and the semiconductor properties of the pyrite. During the eighth quarter, wet chemical and dry oxidation tests were done on Upper Freeport coal from the Troutville [number sign]2 Mine, Clearfield County, Pennsylvania. In addition electrochemical experiments were done on electrodes prepared from Upper Freeport coal pyrite and Pittsburgh coal pyrite samples provided by the US Bureau of Mines, Pittsburgh Research Center, Pennsylvania.

  6. Electro-spark alloying using graphite electrode on titanium alloy surface for biomedical applications

    NASA Astrophysics Data System (ADS)

    Chang-bin, Tang; Dao-xin, Liu; Zhan, Wang; Yang, Gao

    2011-05-01

    In order to improve the biomedical properties of a titanium alloy surface, electro-spark surface alloying was carried out using a graphite electrode in air, in a nitrogen gas atmosphere and in silicone oil. The morphology and microstructure of the strengthened layers were analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The hardness distributions as a function of depth were measured by a micro-hardness tester. Corrosion resistance capacities of the modified layers were evaluated using potentiodynamic polarization measurements and electrochemical impedance spectroscopy (EIS). In addition, wear resistance and corrosive wear properties in a simulated body fluid (SBF) were studied with a pin-on-disk tribometer. Alloyed layers, completely covering the substrate surface and about 40 μm thick mainly composed of the TiC phase and with strong metallurgical bonding and adhesion to the substrate, were obtained. This can markedly improve hardness and wear resistance of the surface layer of the substrate. In comparison to coatings prepared in air and nitrogen gas atmospheres, the coating produced in silicone oil media exhibits a denser and more perfect surface structure. The wear resistance in air and corrosive wear resistance in SBF solution is the best for the coating produced in silicone oil. For instance, the wear rate in air with a GCr15 steel ball counterpart is reduced by a factor of 29 compared with the original titanium alloy and the corrosive wear rate in SBF solution with a corundum ball can decrease by a factor of 13.8. Simultaneously, the effect of electron-spark surface alloying of the titanium alloy surface on biocompatibility and biological activity was also investigated. The electron-spark surface strengthened layer treated in silicone oil shows good biocompatibility and biological activity, and can help cell attachment to the substrate surface.

  7. Self-assembly of virus-structured high surface area nanomaterials and their application as battery electrodes.

    PubMed

    Royston, Elizabeth; Ghosh, Ayan; Kofinas, Peter; Harris, Michael T; Culver, James N

    2008-02-01

    High area nickel and cobalt surfaces were assembled using modified Tobacco mosaic virus (TMV) templates. Rod-shaped TMV templates (300 x 18 nm) engineered to encode unique cysteine residues were self-assembled onto gold patterned surfaces in a vertically oriented fashion, producing a >10-fold increase in surface area. Electroless deposition of ionic metals onto surface-assembled virus templates produced uniform metal coatings up to 40 nm in thickness. Within a nickel-zinc battery system, the incorporation of virus-assembled electrode surfaces more than doubled the total electrode capacity. When combined, these findings demonstrate that surface-assembled virus templates provide a robust platform for the fabrication of oriented high surface area materials.

  8. Working Electrodes

    NASA Astrophysics Data System (ADS)

    Komorsky-Lovrić, Šebojka

    In electrochemistry an electrode is an electronic conductor in contact with an ionic conductor. The electronic conductor can be a metal, or a semiconductor, or a mixed electronic and ionic conductor. The ionic conductor is usually an electrolyte solution; however, solid electrolytes and ionic melts can be used as well. The term "electrode" is also used in a technical sense, meaning the electronic conductor only. If not specified otherwise, this meaning of the term "electrode" is the subject of the present chapter. In the simplest case the electrode is a metallic conductor immersed in an electrolyte solution. At the surface of the electrode, dissolved electroactive ions change their charges by exchanging one or more electrons with the conductor. In this electrochemical reaction both the reduced and oxidized ions remain in solution, while the conductor is chemically inert and serves only as a source and sink of electrons. The technical term "electrode" usually also includes all mechanical parts supporting the conductor (e.g., a rotating disk electrode or a static mercury drop electrode). Furthermore, it includes all chemical and physical modifications of the conductor, or its surface (e.g., a mercury film electrode, an enzyme electrode, and a carbon paste electrode). However, this term does not cover the electrolyte solution and the ionic part of a double layer at the electrode/solution interface. Ion-selective electrodes, which are used in potentiometry, will not be considered in this chapter. Theoretical and practical aspects of electrodes are covered in various books and reviews [1-9].

  9. Static Electrode DC Resistivity Measurement at Surface Water for Pond Subsurface Layer Imaging

    NASA Astrophysics Data System (ADS)

    Sumintadireja, P.; Irawan, D.

    2016-01-01

    Resistivity methods in marine applications show slightly different processing techniques from land based resistivity surveys. Special DC resistivity instruments need to overcome difficulties in arranging the electrode with straight array lines and position. Some geoelectrical instrument manufacturers developed equipment which is able to measure resistivity values and positions in real time. In this paper we demonstrate an application of ordinary geoelectrical instruments for resistivity acquisition in water environment. This study is motivated by the inability to apply conventional DC resistivity instruments in water environment. Land resistivity survey array is arranged on the surface of water using static electrode mode. The method has been tested in various environments, such as ponds/lakes with quiet until rough waves and also measurements at coastal environments. Measurement at the ponds/lakes water environment resulted in data that are almost identic to the measurements obtained using standard land DC resistivity method. On the other hand the measurement in coastal environment does not work properly, possibly due to the lack of power source.

  10. Effect of electrode location on surface electromyography changes due to eccentric elbow flexor exercise.

    PubMed

    Piitulainen, Harri; Bottas, Reijo; Linnamo, Vesa; Komi, Paavo; Avela, Janne

    2009-10-01

    Experiments were carried out to determine whether the location of electrodes has an effect on eccentric exercise-induced changes in surface electromyography (sEMG) variables in the biceps brachii muscle. sEMG signals were recorded with a grid of 64 electrodes before and up to 4 days post-exercise. Root mean square (RMS) and mean power frequency (MNF) were calculated for: (1) each channel; (2) as an average of all channels; and (3) as an average of individual channel rows and columns. Mean muscle-fiber conduction velocity (CV) was estimated similarly but was based on double-differential channels. Maximal isometric voluntary torque decreased 21.3 +/- 5.6% post-exercise. The average sEMG variables decreased after the exercise and recovered 2 days (RMS and CV) or 4 days (MNF) post-exercise. Site-dependent changes were observed in sEMG variables. We conclude that site-dependent changes in sEMG variables after eccentric exercise can be detected and are influenced in part by anatomical factors.

  11. High specific surface gold electrode on polystyrene substrate: Characterization and application as DNA biosensor.

    PubMed

    Yang, Zhiliu; Liu, Yichen; Lu, Wei; Yuan, Qingpan; Wang, Wei; Pu, Qiaosheng; Yao, Bo

    2016-05-15

    In the past decades, many efforts have been made to improve the sensitivity and specificity of electrochemical DNA biosensors. However, it is still strongly required to develop disposable and reliable DNA biosensors for wide and practical application. In this article, we reported superior electrochemical properties of an integrated plastic-gold electrode (PGE) fabricated in-house by chemical plating on polystyrene substrate. PGEs were found having extremely high capacity of DNA immobilization compared with gold electrodes fabricated by standard sputtering based photolithography. Unique nano-structured surface was observed on PGEs through morphology techniques, which would to some extend give an explanation to higher capacity of DNA immobilization on PGEs. A probable mechanism of carboxylic acid produced on polystyrene substrate after exposure to UV irradiation was proposed and discussed for the first time. This biosensor was applied to detection and manipulate of DNA hybridization. Detection limit of 7.2×10(-11) M and 1-500 nM of linearity range was obtained.

  12. Rapid bench-top fabrication of poly(dimethylsiloxane)/polystyrene microfluidic devices incorporating high-surface-area sensing electrodes

    PubMed Central

    Sonney, Sanjay; Shek, Norman; Moran-Mirabal, Jose M.

    2015-01-01

    The development of widely applicable point-of-care sensing and diagnostic devices can benefit from simple and inexpensive fabrication techniques that expedite the design, testing, and implementation of lab-on-a-chip devices. In particular, electrodes integrated within microfluidic devices enable the use of electrochemical techniques for the label-free detection of relevant analytes. This work presents a novel, simple, and cost-effective bench-top approach for the integration of high surface area three-dimensional structured electrodes fabricated on polystyrene (PS) within poly(dimethylsiloxane) (PDMS)-based microfluidics. Optimization of PS-PDMS bonding results in integrated devices that perform well under pressure and fluidic flow stress. Furthermore, the fabrication and bonding processes are shown to have no effect on sensing electrode performance. Finally, the on-chip sensing capabilities of a three-electrode electrochemical cell are demonstrated with a model redox compound, where the high surface area structured electrodes exhibit ultra-high sensitivity. We propose that the developed approach can significantly expedite and reduce the cost of fabrication of sensing devices where arrays of functionalized electrodes can be used for point-of-care analysis and diagnostics. PMID:25945145

  13. Liquid electrode

    DOEpatents

    Ekechukwu, Amy A.

    1994-01-01

    A dropping electrolyte electrode for use in electrochemical analysis of non-polar sample solutions, such as benzene or cyclohexane. The liquid electrode, preferably an aqueous salt solution immiscible in the sample solution, is introduced into the solution in dropwise fashion from a capillary. The electrolyte is introduced at a known rate, thus, the droplets each have the same volume and surface area. The electrode is used in making standard electrochemical measurements in order to determine properties of non-polar sample solutions.

  14. Three-dimensionally ordered macroporous nitroxide polymer brush electrodes prepared by surface-initiated atom transfer polymerization for organic radical batteries.

    PubMed

    Lin, Chun-Hao; Chou, Wei-Jen; Lee, Jyh-Tsung

    2012-01-01

    The synthesis and electrochemical performance of three-dimensionally ordered macroporous (3DOM) nitroxide polymer brush electrodes for organic radical batteries are reported. The 3DOM electrodes are synthesized via polystyrene colloidal crystal templating with electropolymerization of polypyrrole, modification of surface initiator, and surface-initiated atom transfer radical polymerization. The discharge capacity of the 3DOM electrodes is proportional to the thickness of the inverse opal. The discharge capacity of the 3DOM electrode at a discharge rate of 5 C is 40 times higher than that of the planar electrode; its cycle-life performance exhibits 96.1% retention after 250 cycles.

  15. Surface morphology of titanium dioxide (TiO2) nanoparticles on aluminum interdigitated device electrodes (IDEs)

    NASA Astrophysics Data System (ADS)

    Azizah, N.; Hashim, U.; Arshad, M. K. Md.; Gopinath, Subash C. B.; Nadzirah, Sh.; Farehanim, M. A.; Fatin, M. F.; Ruslinda, A. R.; Ayub, R. M.

    2016-07-01

    Titanium dioxide (TiO2) nanoparticles based Interdigitated Device Electrodes (IDEs) Nanobiosensor device was developed for intracellular biochemical detection. Fabrication and characterization of Scanning Electron Microscopy (SEM) using IDE nanocoated with TiO2 was studied in this paper. SEM analysis was carried out at 10 kV acceleration volatege and a 9.8 mA emission current to compare IDE with and without TiO2 on the surface area. The simple fabrication process, high sensitivity, and fast response of the TiO2 based IDEs facilitate their applications in a wide range of areas. The small size of semiconductor TiO2 based IDE for sensitive, label-free, real time detection of a wide range of biological species could be explored in vivo diagnostics and array-based screening.

  16. Poly(3,4-ethylenedioxythiophene) growth on the surface of horizontally aligned MWCNT electrode

    NASA Astrophysics Data System (ADS)

    Krukiewicz, Katarzyna; Bulmer, John S.; Janas, Dawid; Koziol, Krzysztof K. K.; Zak, Jerzy K.

    2015-04-01

    The process of conjugated polymer deposition on the surface of horizontally aligned multi-walled carbon nanotube, HA-CNT, electrode is described. Poly(3,4-ethylenedioxythiophene), PEDOT, was grown electrochemically under variable conditions in both aqueous and non-aqueous solutions of selected electrolytes. It is shown that the mechanism of nucleation highly depends on the reaction environment. The presence of a surfactant or non-aqueous medium favors the process of progressive nucleation in which the polymer growth is uniform and a homogeneous film of PEDOT is formed. It is demonstrated that the conditions make it is possible to cover the outer walls of individual HA-CNTs instead of forming thick polymer layer. The application of overpotential is proven to be a necessary condition to generate radical cations and cause relatively fast growth of polymer layer.

  17. High surface area electrodes in ionic polymer transducers: Numerical and experimental investigations of the electro-chemical behavior

    NASA Astrophysics Data System (ADS)

    Akle, Barbar J.; Habchi, Wassim; Wallmersperger, Thomas; Akle, Etienne J.; Leo, Donald J.

    2011-04-01

    Ionomeric polymer transducer (IPT) is an electroactive polymer that has received considerable attention due to its ability to generate large bending strain (>5%) and moderate stress at low applied voltages (±2 V). Ionic polymer transducers consist of an ionomer, usually Nafion, sandwiched between two electrically conductive electrodes. A novel fabrication technique denoted as the direct assembly process (DAP) enabled controlled electrode architecture in ionic polymer transducers. A DAP built transducer consists of two high surface area electrodes made of electrically conducting particles uniformly distributed in an ionomer matrix sandwiching an ionomer membrane. The purpose of this paper is to investigate and simulate the effect of these high surface area particles on the electro-chemical response of an IPT. Theoretical investigations as well as experimental verifications are performed. The model used consists of a convection-diffusion equation describing the chemical field as well as a Poisson equation describing the electrical field. The two-dimensional model incorporates highly conductive particles randomly distributed in the electrode area. Traditionally, these kinds of electrodes were simulated with boundary conditions representing flat electrodes with a large dielectric permittivity at the polymer boundary. This model enables the design of electrodes with complicated geometrical patterns. In the experimental section, several transducers are fabricated using the DAP process on Nafion 117 membranes. The architecture of the high surface area electrodes in these samples is varied. The concentration of the high surface area RuO2 particles is varied from 30 vol% up to 60 vol% at a fixed thickness of 30 μm, while the overall thickness of the electrode is varied from 10 μm up to 40 μm at a fixed concentration of 45%. The flux and charge accumulation in the materials are measured experimentally and compared to the results of the numerical simulations. Trends of

  18. The Electrode as Organolithium Reagent: Catalyst-Free Covalent Attachment of Electrochemically Active Species to an Azide-Terminated Glassy Carbon Electrode Surface

    SciTech Connect

    Das, Atanu K.; Engelhard, Mark H.; Liu, Fei; Bullock, R. Morris; Roberts, John A.

    2013-12-02

    Glassy carbon electrodes have been activated for modification with azide groups and subsequent coupling with ferrocenyl reagents by a catalyst-free route using lithium acetylide-ethylenediamine complex, and also by the more common Cu(I)-catalyzed alkyne-azide coupling (CuAAC) route, both affording high surface coverages. Electrodes were preconditioned at ambient temperature under nitrogen, and ferrocenyl surface coverages obtained by CuAAC were comparable to those reported with preconditioning at 1000 °C under hydrogen/nitrogen. The reaction of lithium acetylide-ethylenediamine with the azide-terminated electrode affords a 1,2,3-triazolyllithium-terminated surface that is active toward covalent C-C coupling reactions including displacement at an aliphatic halide and nucleophilic addition at an aldehyde. For example, surface ferrocenyl groups were introduced by reaction with (6-iodohexyl)ferrocene; the voltammetry shows narrow, symmetric peaks indicating uniform attachment. Coverages are competitive with those obtained by the CuAAC route. X-ray photoelectron spectroscopic data, presented for each synthetic step, are consistent with the proposed reactions. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. A portion of the research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

  19. A novel bioelectrochemical interface based on in situ synthesis of gold nanostructures on electrode surfaces and surface activation by Meerwein's salt. A bioelectrochemical sensor for glucose determination.

    PubMed

    Nikolaev, Konstantin; Ermakov, Sergey; Ermolenko, Yuri; Averyaskina, Elena; Offenhäusser, Andreas; Mourzina, Yulia

    2015-10-01

    A novel effective bioelectrochemical sensor interface for enzyme biosensors is proposed. The method is based on in situ synthesis of gold nanostructures (5-15 nm) on the thin-film electrode surface using the oleylamine (OA) method, which provides a high-density, stable, electrode interface nanoarchitecture. New method to activate the surface of the OA-stabilized nanostructured electrochemical interface for further functionalization with biomolecules (glucose oxidase enzyme) using Meerwein's salt is proposed. Using this approach a new biosensor for glucose determination with improved analytical characteristics: wide working range of 0.06-18.5mM with a sensitivity of 22.6 ± 0.5 μAmM(-1)cm(-2), limit of detection 0.02 mM, high reproducibility, and long lifetime (60 d, 93%) was developed. The surface morphology of the electrodes was characterized by scanning electron microscopy (SEM). The electrochemical properties of the interface were studied by cyclic voltammetry and electrochemical impedance spectroscopy using a Fe(II/III) redox couple. The studies revealed an increase in the electroactive surface area and a decrease in the charge transfer resistance following surface activation with Meerwein's reagent. A remarkably enhanced stability and reproducibility of the sensor was achieved using in situ synthesis of gold nanostructures on the electrode surface, while surface activation with Meerwein's salt proved indispensable in achieving an efficient bioelectrochemical interface. PMID:25983284

  20. Effects of the surface mobility on the oxidation of adsorbed CO on platinum electrodes in alkaline media. The role of the adlayer and surface defects.

    PubMed

    Herrero, Enrique; Chen, Qing-Song; Hernández, Javier; Sun, Shi-Gang; Feliu, Juan M

    2011-10-01

    The oxidation of adsorbed CO on Pt single crystal electrodes has been studied in alkaline media. The surfaces used in this study were the Pt(111) electrode and vicinal stepped and kinked surfaces with (111) terraces. The kinked surfaces have either (110) steps broken by (100) kinks or (100) steps broken by (110) kinks and different kink densities. The voltammetric profiles for the CO stripping on those electrodes show peaks corresponding to the oxidation of CO on the (111) terraces, on the (100) steps/kinks and on the (110) steps/kinks at very distinctive potentials. Additionally, the stripping voltammograms always present a prewave. The analysis of the results with the different stepped and kinked surfaces indicates that the presence of the prewave is not associated with defects or kinks in the electrode surface. Also, the clear separation of the CO stripping process in different peak contributions indicates that the mobility of CO on the surface is very low. Using partial CO stripping experiments and studies at different pH, it has been proposed that the low mobility is a consequence of the negative absolute potential at which the adlayers are formed in alkaline media. Also, the surface diffusion coefficient for CO in these media has been estimated from the dependence of the stripping charge of the peaks with the scan rate of the voltammetry. PMID:21863178

  1. Quantum information experiments with a micro-fabricated, cryogenic, surface-electrode ion trap

    NASA Astrophysics Data System (ADS)

    Wilson, A. C.; Brown, K. R.; Ospelkaus, C.; Colombe, Y.; Leibfried, D.; Wineland, D. J.

    2011-05-01

    Although the basic components of a quantum information processor using trapped ions have been demonstrated, scaling to large numbers of qubits and operations so that algorithms and simulations of practical importance can be implemented remains a major challenge. This is technically challenging because it requires significant improvements in the precision with which quantum states of ions are prepared, manipulated and measured. Solutions are multi-disciplinary - involving micro-fabrication, cryogenics, integrated photonic devices, as wells as materials and surface science. Here we report progress from experiments that address a range of these issues. We use a micro-fabricated, cryogenic, surface-electrode ion trap, with two closely-spaced independently controlled potential wells. In the first experiment with this new apparatus, we implement a scheme for coupling two ions trapped in separate wells, and demonstrate tunable energy exchange at approximately the single quantum level. A second experiment investigates errors in single qubit gates (rotations) with the use of randomized bench-marking. Although the basic components of a quantum information processor using trapped ions have been demonstrated, scaling to large numbers of qubits and operations so that algorithms and simulations of practical importance can be implemented remains a major challenge. This is technically challenging because it requires significant improvements in the precision with which quantum states of ions are prepared, manipulated and measured. Solutions are multi-disciplinary - involving micro-fabrication, cryogenics, integrated photonic devices, as wells as materials and surface science. Here we report progress from experiments that address a range of these issues. We use a micro-fabricated, cryogenic, surface-electrode ion trap, with two closely-spaced independently controlled potential wells. In the first experiment with this new apparatus, we implement a scheme for coupling two ions trapped

  2. A nonmonotonic dependence of standard rate constant on reorganization energy for heterogeneous electron transfer processes on electrode surface

    NASA Astrophysics Data System (ADS)

    Xu, Weilin; Li, Songtao; Zhou, Xiaochun; Xing, Wei; Huang, Mingyou; Lu, Tianhong; Liu, Changpeng

    2006-05-01

    In the present work a nonmonotonic dependence of standard rate constant (k0) on reorganization energy (λ) was discovered qualitatively from electron transfer (Marcus-Hush-Levich) theory for heterogeneous electron transfer processes on electrode surface. It was found that the nonmonotonic dependence of k0 on λ is another result, besides the disappearance of the famous Marcus inverted region, coming from the continuum of electronic states in electrode: with the increase of λ, the states for both Process I and Process II ET processes all vary from nonadiabatic to adiabatic state continuously, and the λ dependence of k0 for Process I is monotonic thoroughly, while for Process II on electrode surface the λ dependence of k0 could show a nonmonotonicity.

  3. Assembling Paramagnetic Ceruloplasmin at Electrode Surfaces Covered with Ferromagnetic Nanoparticles. Scanning Electrochemical Microscopy in the Presence of a Magnetic Field.

    PubMed

    Matysiak, Edyta; Botz, Alexander J R; Clausmeyer, Jan; Wagner, Barbara; Schuhmann, Wolfgang; Stojek, Zbigniew; Nowicka, Anna M

    2015-07-28

    Adsorption of ceruloplasmin (Cp) at a gold electrode modified with ferromagnetic iron nanoparticles encapsulated in carbon (Fe@C Nps) leads to a successful immobilization of the enzyme in its electroactive form. The proper placement of Cp at the electrode surface on top of the nanocapsules containing an iron core allowed a preorientation of the enzyme, hence allowing direct electron transfer between the electrode and the enzyme. Laser ablation coupled with inductively coupled plasma mass spectrometry indicated that Cp was predominantly located at the paramagnetic nanoparticles. Scanning electrochemical microscopy measurements in the sample-generation/tip-collection mode proved that Cp was ferrooxidative inactive if it was immobilized on the bare gold surface and reached the highest activity if it was adsorbed on Fe@C Nps in the presence of a magnetic field.

  4. Surface acidity scales: Experimental measurements of Brønsted acidities on anatase TiO2 and comparison with coinage metal surfaces

    NASA Astrophysics Data System (ADS)

    Silbaugh, Trent L.; Boaventura, Jaime S.; Barteau, Mark A.

    2016-08-01

    The first quantitative surface acidity scale for Brønsted acids on a solid surface is presented through the use of titration-displacement and equilibrium experiments on anatase TiO2. Surface acidities of species on TiO2 correlated with gas phase acidities, as was previously observed in qualitative studies of Brønsted acid displacement on Ag(110), Cu(110) and Au(111). A 90% compression of the surface acidity scale relative to the gas phase was observed due to compensation from the covalent component of the conjugate base - surface bond. Adsorbed conjugate bases need not be completely anionic for correlations with gas phase acidities to hold. Positive and negative substituent effects, such as substituted fluorine and hydrocarbon sidechain dispersion interactions with the surface, may modify the surface acidity scale, in agreement with previous experimental and theoretical work on Au(111).

  5. Comparison of the potential dependence of the surface-enhanced raman effect at colloid silver particles and bulk silver electrodes

    NASA Astrophysics Data System (ADS)

    Wetzel, H.; Gerischer, H.; Pettinger, B.

    1982-01-01

    The potential dependence of surface-enhanccd Raman signals from pyridine adsorbed onto silver sol particles is identical to that from pyridine adsorbed on flat silver electrodes. Variation of the potential at the interface silver sol particle/electrolyte was achieved by adding the redox system europiums 3+/europium 2+ and varying the concentration ratio.

  6. Voltammetric studies of Azathioprine on the surface of graphite electrode modified with graphene nanosheets decorated with Ag nanoparticles.

    PubMed

    Asadian, Elham; Iraji Zad, Azam; Shahrokhian, Saeed

    2016-01-01

    By using graphene nanosheets decorated with Ag nanoparticles (AgNPs-G) as an effective approach for the surface modification of pyrolytic graphite electrode (PGE), a sensing platform was fabricated for the sensitive voltammetric determination of Azathioprine (Aza). The prepared AgNPs-G nanosheets were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-vis and Raman spectroscopy techniques. The electrochemical behavior of Aza was investigated by means of cyclic voltammetry. Comparing to the bare PGE, a remarkable enhancement was observed in the response characteristics of Aza on the surface of the modified electrode (AgNPs-G/PGE) as well as a noticeable decrease in its reduction overpotential. These results can be attributed to the incredible enlargement in the microscopic surface area of the electrode due to the presence of graphene nanosheets together with strong adsorption of Aza on its surface. The effect of experimental parameters such as accumulation time, the amount of modifier suspension and pH of the supporting electrolyte were also optimized toward obtaining the maximum sensitivity. Under the optimum conditions, the calibration curve studies demonstrated that the peak current increased linearly with Aza concentrations in the range of 7 × 10(-7) to 1 × 10(-4)mol L(-1) with the detection limit of 68 nM. Further experiments revealed that the modified electrode can be successfully applied for the accurate determination of Aza in pharmaceutical preparations.

  7. Syntheses of Hemoprotein Models that can be Covalently Attached onto Electrode Surfaces by “Click” Chemistry

    PubMed Central

    Decréau, Richard A.; Collman, James P.; Yang, Ying; Yan, Yilong; Devaraj, Neal K.

    2008-01-01

    Five alkyne-containing hemoprotein models have been synthesized in a convergent manner. Sonogashira coupling was used to introduce the alkyne functional group on the proximal imidazole before or after being attached on the porphyrin. One model was immobilized onto a gold electrode surface via copper(I) catalyzed azide-alkyne cycloaddition (Sharpless Click Chemistry). PMID:17375955

  8. Corrosion behavior of surface treated steel in liquid sodium negative electrode of liquid metal battery

    NASA Astrophysics Data System (ADS)

    Lee, Jeonghyeon; Shin, Sang Hun; Lee, Jung Ki; Choi, Sungyeol; Kim, Ji Hyun

    2016-03-01

    While liquid metal batteries are attractive options for grid-scale energy storage applications as they have flexible siting capacities and small footprints, the compatibility between structural materials such as current collectors and negative electrode such as sodium is one of major issues for liquid metal batteries. Non-metallic elements such as carbon, oxygen, and nitrogen in the liquid sodium influence the material behaviors of the cell construction materials in the battery system. In this study, the compatibility of structural materials with sodium is investigated in high temperature liquid sodium, and electrochemical impedance spectroscopy (EIS) is used to monitor in-situ the corrosion behavior at the surface of materials in sodium. Chemical vapor deposition (CVD) coatings of SiC and Si3N4 are applied as protective barriers against dissolution and corrosion on the steel surface. The results show that CVD coating of Si compounds can delay corrosion of steel in high temperature liquid sodium comparing to the result of as-received specimens, while SiC coating is more durable than Si3N4 coating in high temperature liquid sodium.

  9. Contribution of specifically adsorbed ions, water, and impurities to the surface enhanced Raman spectroscopy (SERS) of Ag electrodes

    NASA Astrophysics Data System (ADS)

    Pettinger, Bruno; Philpott, Michael R.; Gordon, Joseph G., II

    1981-01-01

    Surface enhanced Raman scattering (SERS) has been observed from silver electrodes for water (H2O and D2O) in the frequency region of the librational, bending, and stretching modes. Simultaneously, SERS has been observed for halide ions and some organic impurities. The appearance of SERS from water and halide ions under the circumstances of the experiment is attributed to the formation of surface complexes involving silver adatoms, halide ions, and water molecules.

  10. Volume-surface barrier discharge in dried air in three-electrode system fed by impulse high voltage with nanosecond rise time

    NASA Astrophysics Data System (ADS)

    Malashin, Maxim; Rebrov, Igor; Nebogatkin, Sergey; Sokolova, Marina; Nikitin, Alexey; Voevodin, Vadim; Krivov, Sergey

    2016-08-01

    Results of experimental investigation of a volume-surface barrier discharge in a three-electrode system under periodic impulse voltage applied to the surface discharge (SD) electrodes and a d.c. potential applied to an additional third electrode are presented. It is shown that there is a strong influence of polarity and amplitude of the d.c. potential on the direct current "extracted" out of the surface discharge plasma layer by electric field of the third electrode. The amount of charged positive species that constitute the "extracted" current prevails under positive impulse voltage for low values of the negative d.c. potential of the third electrode. The amount of negative species prevails with higher values of the positive d.c. positive of the third electrode. Contribution to the topical issue "6th Central European Symposium on Plasma Chemistry (CESPC-6)", edited by Nicolas Gherardi, Ester Marotta and Cristina Paradisi

  11. Enhancing on-surface mismatch discrimination capability of PNA probes by AuNP modification of gold(111) surface.

    PubMed

    Ghosh, Srabani; Mishra, Sourav; Mukhopadhyay, Rupa

    2013-09-24

    Unambiguous identification of single base mismatches in nucleic acid sequences is of great importance in nucleic acid detection assays. However, ambiguities are often encountered with, and therefore, a strategy for attaining substantially large enhancement of mismatch discrimination has been worked upon in this study. Short single-stranded peptide nucleic acid (PNA) and deoxyribonucleic acid (DNA) sensor probes that are immobilized onto gold nanoparticle (AuNP) modified Au(111) surface have been applied for target DNA detection. It will be shown that while both PNA and the analogous DNA probes exhibit generally better target detection abilities on the AuNP-modified Au(111) surface (elicited from fluorescence-based measurement of on-surface Tm values), compared to the bare Au(111) surface, PNA supersedes DNA, for all sizes of AuNPs (10, 50, and 90 nm) applied, with the difference being quite drastic in the case of the smallest 10 nm AuNP. It is found that while the AuNP curvature plays a pivotal role in target detection abilities of the PNA probes, the changes in the surface roughness caused by AuNP treatment do not exert any significant influence. This study also presents a means for preparing PNA-AuNP hybrids without altering PNA functionality and without AuNP aggregation by working with the surface-affixed AuNPs.

  12. Iron porphyrin polymer films: Materials for the modification of electrode surfaces and the detection of nitric oxide

    SciTech Connect

    McGuire, M.; Drew, S.M.

    1996-10-01

    We are currently investigating a new method for the detection and quantification of nitric oxide (NO) based on a carbon electrode chemically modified with an iron porphyrin polymer film. Commercially available vinyl-substituted iron porphyrin monomers can be polymerized directly onto electrode surfaces through a published electrochemical polymerization process. We are also developing a synthesis for a new vinyl-substituted monomer, iron 5,10,15-triphenyl-20-vinyl porphyrin chloride, in hopes of improving polymer film stability. The electrochemistry of NO is also being investigated at electrodes chemically modified with an iron porphyrin polymer film. We are studying the catalytic oxidation of iron porphyrin bound NO to nitrate by molecular oxygen. The reaction with molecular oxygen is preceded by a one electron reduction of the iron porphyrin-NO complex. If currents proportional to nitric oxide concentration can be measured, a new NO electrochemical sensor will be designed.

  13. Surface and Electrical Characterization of Ag/AgCl Pseudo-Reference Electrodes Manufactured with Commercially Available PCB Technologies.

    PubMed

    Moschou, Despina; Trantidou, Tatiana; Regoutz, Anna; Carta, Daniela; Morgan, Hywel; Prodromakis, Themistoklis

    2015-07-24

    Lab-on-Chip is a technology that could potentially revolutionize medical Point-of-Care diagnostics. Considerable research effort is focused towards innovating production technologies that will make commercial upscaling financially viable. Printed circuit board manufacturing techniques offer several prospects in this field. Here, we present a novel approach to manufacturing Printed Circuit Board (PCB)-based Ag/AgCl reference electrodes, an essential component of biosensors. Our prototypes were characterized both structurally and electrically. Scanning Electron Microscopy (SEM) and X-Ray Photoelectron Spectroscopy (XPS) were employed to evaluate the electrode surface characteristics. Electrical characterization was performed to determine stability and pH dependency. Finally, we demonstrate utilization along with PCB pH sensors, as a step towards a fully integrated PCB platform, comparing performance with discrete commercial reference electrodes.

  14. Surface and Electrical Characterization of Ag/AgCl Pseudo-Reference Electrodes Manufactured with Commercially Available PCB Technologies

    PubMed Central

    Moschou, Despina; Trantidou, Tatiana; Regoutz, Anna; Carta, Daniela; Morgan, Hywel; Prodromakis, Themistoklis

    2015-01-01

    Lab-on-Chip is a technology that could potentially revolutionize medical Point-of-Care diagnostics. Considerable research effort is focused towards innovating production technologies that will make commercial upscaling financially viable. Printed circuit board manufacturing techniques offer several prospects in this field. Here, we present a novel approach to manufacturing Printed Circuit Board (PCB)-based Ag/AgCl reference electrodes, an essential component of biosensors. Our prototypes were characterized both structurally and electrically. Scanning Electron Microscopy (SEM) and X-Ray Photoelectron Spectroscopy (XPS) were employed to evaluate the electrode surface characteristics. Electrical characterization was performed to determine stability and pH dependency. Finally, we demonstrate utilization along with PCB pH sensors, as a step towards a fully integrated PCB platform, comparing performance with discrete commercial reference electrodes. PMID:26213940

  15. Surface study of stainless steel electrode deposition from soil electrokinetic (EK) treatment using X-ray photoelectron spectroscopy (XPS)

    SciTech Connect

    Embong, Zaidi; Johar, Saffuwan; Tajudin, Saiful Azhar Ahmad; Sahdan, Mohd Zainizan

    2015-04-29

    Electrokinetic (EK) remediation relies upon application of a low-intensity direct current through the soil between stainless steel electrodes that are divided into a cathode array and an anode array. This mobilizes charged species, causing ions and water to move toward the electrodes. Metal ions and positively charged organic compounds move toward the cathode. Anions such as chloride, fluoride, nitrate, and negatively charged organic compounds move toward the anode. Here, this remediation techniques lead to a formation of a deposition at the both cathode and anode surface that mainly contributed byanion and cation from the remediated soil. In this research, Renggam-Jerangau soil species (HaplicAcrisol + RhodicFerralsol) with a surveymeter reading of 38.0 ± 3.9 μR/hr has been investigation in order to study the mobility of the anion and cation under the influence electric field. Prior to the EK treatment, the elemental composition of the soil and the stainless steel electrode are measured using XRF analyses. Next, the soil sample is remediated at a constant electric potential of 30 V within an hour of treatment period. A surface study for the deposition layer of the cathode and anode using X-ray Photoelectron spectroscopy (XPS) revealed that a narrow photoelectron signal from oxygen O 1s, carbon, C 1s silica, Si 2p, aluminium, Al 2p and chromium, Cr 2p exhibited on the electrode surface and indicate that a different in photoelectron intensity for each element on both electrode surface. In this paper, the mechanism of Si{sup 2+} and Al{sup 2+} cation mobility under the influence of voltage potential between the cathode and anode will be discussed in detail.

  16. Surface study of stainless steel electrode deposition from soil electrokinetic (EK) treatment using X-ray photoelectron spectroscopy (XPS)

    NASA Astrophysics Data System (ADS)

    Embong, Zaidi; Johar, Saffuwan; Tajudin, Saiful Azhar Ahmad; Sahdan, Mohd Zainizan

    2015-04-01

    Electrokinetic (EK) remediation relies upon application of a low-intensity direct current through the soil between stainless steel electrodes that are divided into a cathode array and an anode array. This mobilizes charged species, causing ions and water to move toward the electrodes. Metal ions and positively charged organic compounds move toward the cathode. Anions such as chloride, fluoride, nitrate, and negatively charged organic compounds move toward the anode. Here, this remediation techniques lead to a formation of a deposition at the both cathode and anode surface that mainly contributed byanion and cation from the remediated soil. In this research, Renggam-Jerangau soil species (HaplicAcrisol + RhodicFerralsol) with a surveymeter reading of 38.0 ± 3.9 μR/hr has been investigation in order to study the mobility of the anion and cation under the influence electric field. Prior to the EK treatment, the elemental composition of the soil and the stainless steel electrode are measured using XRF analyses. Next, the soil sample is remediated at a constant electric potential of 30 V within an hour of treatment period. A surface study for the deposition layer of the cathode and anode using X-ray Photoelectron spectroscopy (XPS) revealed that a narrow photoelectron signal from oxygen O 1s, carbon, C 1s silica, Si 2p, aluminium, Al 2p and chromium, Cr 2p exhibited on the electrode surface and indicate that a different in photoelectron intensity for each element on both electrode surface. In this paper, the mechanism of Si2+ and Al2+ cation mobility under the influence of voltage potential between the cathode and anode will be discussed in detail.

  17. Soft X-ray absorption spectroscopic studies with different probing depths: Effect of an electrolyte additive on electrode surfaces

    NASA Astrophysics Data System (ADS)

    Yogi, Chihiro; Takamatsu, Daiko; Yamanaka, Keisuke; Arai, Hajime; Uchimoto, Yoshiharu; Kojima, Kazuo; Watanabe, Iwao; Ohta, Toshiaki; Ogumi, Zenpachi

    2014-02-01

    A solid electrolyte interphase (SEI) formed on a model LiCoO2 electrode was analyzed by the ultra-soft X-ray absorption spectroscopy (XAS). The data of Li K-, B K-, C K-, O K-, and Co L-edges spectra for the SEI film on the electrode were collected using three detection methods with different probing depths. The electrode was prepared by a pulsed laser deposition method. All the spectral data consistently indicated that the SEI film containing lithium carbonate was instantly formed just after the soak of the electrode into the electrolyte solution and that it decomposed during the repeated charge-discharge reactions. The decomposition of the SEI film seems to cause the deterioration in lithium ion battery cycle performance. By adding lithium bis(oxalate) borate (LiBOB) to the electrolyte the decomposition could be suppressed leading to longer cycle life. It was found that some of the Co ions at the electrode surface were reduced to Co(II) during the charge-discharge reactions and this reaction could also be suppressed by the addition of LiBOB.

  18. Electrical characterization of gold and platinum thin film electrodes with polyaniline modified surfaces

    NASA Astrophysics Data System (ADS)

    Aggas, John Richard

    Recent studies into soft organic electronics have burgeoned as a result of discoveries of conducting polymers such as polyaniline, polythiophene, and polypyrrole. However, in order to make these conducting polymers suitable for in vivo soft organic electronics, they must be developed so that they can be biocompatible and provide accurate sensing. Chitosan, a naturally occurring polymer structure found in exoskeletons of crustaceans, has been studied for its biocompatible properties. Composites of polyaniline (PAn), an intrinsically conductive polymer (ICP) and chitosan (Chi), a biopolymer, were developed and applied to gold and platinum Thin Film Electrode (TFE) devices. Electropolymerization and drop cast deposition were utilized to modify TFEs with a thin film of PAn or PAn-Chi composite. The impedance response over a spectrum of frequencies was studied for blank control TFEs, platinized TFEs, and platinized TFEs with various polyaniline coatings. Impedance measurements were taken in dry environments, DI Water, and in buffers such as PBS, and HEPES. Current-Voltage (I-V) characterization was used to study the current response and SEM imaging was used to study the surface topography. Resistance was measured for PAn modified unplatinized gold TFEs with varying amounts of incorporated chitosan. Impedance measurements of control and platinized TFEs yielded results similar to a low pass filter. Due to the conductive nature of polyaniline, the impedance of TFEs decreased substantially after poylaniline deposition. Measured resistance values for polyaniline and chitosan composites on TFEs revealed a window of concentrations of incorporated chitosan to lower resistance.

  19. Polydivinylferrocene surface modified electrode for measuring state-of-charge of lead-acid battery

    NASA Astrophysics Data System (ADS)

    Lee, Todd; Singh, Pritam; Baker, Murray V.; Issa, Touma B.

    This paper outlines an investigation of the electrochemical behaviour of polymeric divinylferrocene (PDVF) produced by direct polymerisation of divinylferrocene (DVF) monomer on a glassy carbon substrate. The findings indicate that PDVF undergoes reversible reduction/oxidation in neutral and acidic aqueous media containing perchlorate (ClO 4 -) and sulfhate (SO 4 2-). The anodic peak potential of the PDVF shifts linearly to less positive potentials as the sulfuric acid (H 2SO 4) concentration is increased from 1 to 5 M. The polymer film strongly adheres to the glassy carbon surface and is electrochemically stable when subjected to repeated voltammetric cycling in the potential range of -0.2 to +0.8 V vs. Ag|AgCl. The potential of the partially oxidized film of PVDF on a glassy carbon substrate against a Ag|AgCl/KCl reference electrode in sulfuric acid solution is stable, reproducible and varies linearly with the acid concentration in the range of 1-5 M. This observation may be suitable for potentiometrically measuring the state-of-charge of lead-acid batteries.

  20. One-Step Modification of Electrode Surface for Ultrasensitive and Highly Selective Detection of Nucleic Acids with Practical Applications.

    PubMed

    Li, Chao; Wu, Dan; Hu, Xiaolu; Xiang, Yang; Shu, Yongqian; Li, Genxi

    2016-08-01

    Electrochemistry-based nucleic acid sensors have long been plagued by the limited accessibility of target molecules to the capture probes immobilized on heterogeneous surfaces, which largely hinders their practical application. In this work, we find that dual-thiolated hairpin DNA immobilized on an electrode surface as the capture probe cannot only efficiently bind with target molecule as well as the signal probe but also process impressive protein-repelling ability, which allows us to directly detect as few as attomolar targets (∼300 copies in 100 μL sample) with single-base discrimination ability. Meanwhile, the preparation of functional electrode surface becomes simple (one step), fast (30 min), and homogeneous (just one probe modified surface without small molecules coassembled). These advantages are attributed to the unique probe design, where the stem of the capture probe can act as rigid scaffold to keep it upright, and the loop of the capture probe may provide an enclosed platform for target and signal probe binding. More importantly, through tuning the distance between enzyme and the electrode surface (from 8.5 to 13.6 nm), we find that the performance of the sensor can be favorably controlled. Furthermore, taking advantage of this new binding model, different complex samples including polymerase chain reaction (PCR) product, mRNA, and micro RNA can be conveniently analyzed, which may hold great potential for real application. PMID:27374134

  1. Simulation of Nerve Bundle Activation by Simultaneous Multipoint Extracellular Stimulation with Surface Electrodes

    NASA Astrophysics Data System (ADS)

    Takahashi, Hirokazu; Nakao, Masayuki; Kaga, Kimitaka

    Neural prostheses for restoring lost functions can benefit from selective activation of nerves. We had previously proposed a multiple gating stimulation, which can selectively activate a desired portion of nerve bundle, irrespective of a density of the electrode. In this paper, we discuss the design of electrode array and effective strategies to determine the stimulus parameters. A large electrode was less affected by the relative location of electrodes and the node of Ranvier, suggesting that a rectangular electrode, whose long side along a nerve bundle is longer than the internodal distance, i.e., on the order of 1 mm, would be more effective rather than a disk electrode. We could estimate an appropriate current at each electrode was a blocking threshold. For the lateral gating stimulation, the gate current should be set above the threshold, while, for depth-wise gating stimulation, the gate current should be set below the threshold. The spatial resolution of lateral gating stimulation is theoretically estimated at least at 50 μm when the grid of array was 1.2 mm, and that of depth-wise gating stimulation at 50 μm.

  2. Liquid electrode

    DOEpatents

    Ekechukwu, A.A.

    1994-07-05

    A dropping electrolyte electrode is described for use in electrochemical analysis of non-polar sample solutions, such as benzene or cyclohexane. The liquid electrode, preferably an aqueous salt solution immiscible in the sample solution, is introduced into the solution in dropwise fashion from a capillary. The electrolyte is introduced at a known rate, thus, the droplets each have the same volume and surface area. The electrode is used in making standard electrochemical measurements in order to determine properties of non-polar sample solutions. 2 figures.

  3. Improving neuron-to-electrode surface attachment via alkanethiol self-assembly: an alternating current impedance study.

    PubMed

    Slaughter, Gymama E; Bieberich, Erhard; Wnek, Gary E; Wynne, Kenneth J; Guiseppi-Elie, Anthony

    2004-08-17

    In this work, the omega-amine alkanethiols, cysteamine (CA) and 11-amino-1-undecanethiol (11-AUT), were chemisorbed as self-assembled monolayers (SAMs) onto 250-microm gold microelectrodes that were microlithographically fabricated within eight-well cell culture plates and investigated as a means to improve neuron-to-electrode surface attachment (NESA). Dynamic contact angle (DCA) measurements showed similar advancing, theta(a) (69 degrees and 65 degrees ), but contrasting receding contact angles, theta(r) (9 and 30 degrees ) for CA- and 11-AUT-SAMs, respectively. The corresponding hysteresis (Deltatheta(ar) = 60 and 35 degrees, respectively) indicates the CA-SAM displays greater amphiphilic character than the 11-AUT-SAM. A portion of the greater Deltatheta(ar) for CA-SAMs may arise from surface heterogeneity, as compared to sputter-deposited gold and 11-AUT-SAMs. Tapping mode atomic force microscopy (AFM) confirmed a 6% increase (CA-SAM) and a 22% decrease (11-AUT-SAM) in surface roughness when compared to clean but unmodified, sputter-deposited gold. The extracellular matrix cell adhesion proteins, collagen, fibronectin, and laminin, were covalently coupled to the aminoalkanethiol-decorated gold electrodes via acid-amine heterobifunctional cross-linking. Using fluorescein isothiocyanate-tagged laminin, confocal fluorescence microscopy of both CA- and 11-AUT-SAM-modified and unmodified gold microelectrodes confirmed coupling of the protein to the electrode and was readily distinguishable from nonspecifically adsorbed protein. DCA measurements of laminin physisorbed directly onto gold or covalently immobilized via CA- or 11-AUT-SAM had similar advancing (ca. 63-65 degrees ) and receding (ca. 7-9 degrees ) contact angles. Tapping mode AFM of these protein-bearing surfaces likewise showed dimerized protein aggregates of similar surface roughness. PC-12 cells cultured to confluence on both unmodified and SAM-modified, protein-derivatized gold microelectrodes were

  4. Application of power spectra patterns in Fourier transform square wave voltammetry to evaluate electrode kinetics of surface-confined proteins.

    PubMed

    Fleming, Barry D; Barlow, Nicola L; Zhang, Jie; Bond, Alan M; Armstrong, Fraser A

    2006-05-01

    This paper describes an application of Fourier transform (FT) voltammetry that provides a quantitative evaluation of the electron-transfer kinetics of protein molecules attached to electrode surfaces. The potential waveform applied in these experiments consists of a large-amplitude square wave of frequency f superimposed onto the traditional triangular voltage used in dc cyclic voltammetry. The resultant current-time response, when Fourier transformed into the frequency domain, provides patterns of data at the even harmonic frequencies that arise from nonlinearity in the Faradaic response. These even harmonic contributions are ideally suited for kinetic evaluation of electron-transfer processes because they are highly selective to quasi-reversible behavior (insensitive to reversible or irreversible processes) and almost devoid of background charging current. Inverse FT methods can then be used to provide the wave shapes of the dc as well as the ac voltammetric components and other characteristics employed to detect the level of nonideality present relative to theoretical models based upon noninteracting surface-confined molecules. The new form of data evaluation has been applied to the electron-transfer properties of a typical biological electron carrier, the blue copper protein azurin, immobilized on polycrystalline gold electrodes modified with self-assembled monolayers of different length alkanethiols. Details of the electrode kinetics (rates of electron transfer, dispersion, and charge-transfer coefficients) as a function of alkanethiol, apparent surface coverage, and capacitance are all deduced from the square wave (FT-inverse FT) protocol, and the implications of these findings are considered.

  5. Marcus-Hush-Chidsey theory of electron transfer to and from species bound at a non-uniform electrode surface: Theory and experiment

    NASA Astrophysics Data System (ADS)

    Henstridge, Martin C.; Batchelor-McAuley, Christopher; Gusmão, Rui; Compton, Richard G.

    2011-11-01

    Two simple models of electrode surface inhomogeneity based on Marcus-Hush theory are considered; a distribution in formal potentials and a distribution in electron tunnelling distances. Cyclic voltammetry simulated using these models is compared with that simulated using Marcus-Hush theory for a flat, uniform and homogeneous electrode surface, with the two models of surface inhomogeneity yielding broadened peaks with decreased peak-currents. An edge-plane pyrolytic graphite electrode is covalently modified with ferrocene via 'click' chemistry and the resulting voltammetry compared with each of the three previously considered models. The distribution of formal potentials is seen to fit the experimental data most closely.

  6. Experimental study on magnetically insulated transmission line electrode surface evolution process under MA/cm current density

    NASA Astrophysics Data System (ADS)

    Zhang, PengFei; Hu, Yang; Yang, HaiLiang; Sun, Jiang; Wang, Liangping; Cong, Peitian; Qiu, Aici

    2016-03-01

    The design of high-current density magnetically insulated transmission line (MITL) is a difficult problem of current large-scale Z-pinch device. In particular, a thorough understanding of the MITL electrode surface evolution process under high current density is lacking. On the "QiangGuang-I" accelerator, the load area possesses a low inductance short-circuit structure with a diameter of 2.85 mm at the cathode, and three reflux columns with a diameter of 3 mm and uniformly distributed circumference at the anode. The length of the high density MITL area is 20 mm. A laser interferometer is used to assess and analyze the state of the MITL cathode and anode gap, and their evolution process under high current density. Experimental results indicate that evident current loss is not observed in the current density area at pulse leading edge, and peak when the surface current density reaches MA/cm. Analysis on electrode surface working conditions indicates that when the current leading edge is at 71.5% of the peak, the total evaporation of MITL cathode structure can be realized by energy deposition caused by ohmic heating. The electrode state changes, and diffusion conditions are reflected in the laser interferometer image. The MITL cathode area mainly exists in metal vapor form. The metal vapor density in the cathode central region is higher than the upper limit of laser penetration density (˜4 × 1021/cm3), with an expansion velocity of ˜0.96 km/s. The metal vapor density in the electrode outer area may lead to evident distortion of fringes, and its expansion velocity is faster than that in the center area (1.53 km/s).

  7. [Surface-enhanced Raman spectroscopy of biopolymers: membrane proteins, bacteriorhodopsin and rhodopsin adsorbed on silver electrodes and silver hydrosols].

    PubMed

    Nabiev, I R; Efremov, R G; Chumanov, G D

    1986-01-01

    Surface-enhanced Raman (SER) spectra of purple membranes of Halobacterium halobium and photoreceptor disks of the rod outer segments adsorbed on silver hydrosols were analysed. It has been shown that the intensity of SER spectra of bacterial and visual rhodopsins increases 5 X 10(4) times at adsorption. Concentration relationship of the signal intensity of SER spectra has the maximum at bacteriorhodopsin concentration about 2 X 10(-7) M. It has been shown that adsorption on silver hydrosol leads to fixation of light-induced photochemical transformations in bacterial and visual rhodopsins. Adsorption on the "smooth" electrodes at the potential of the zero charge of silver does not affect the photocycle of bacteriorhodopsin. An increase or decrease of the electrode potential relative to the zero charge point of silver leads to the accumulation of kinetic intermediate K610 and a decrease of the concentration of the form BRh570. It has been shown that on the "smooth" electrode primarily the long-range component of the SER mechanism is realized. Bands corresponding to the vibrations of the atom groups directly contacting with the metal are mainly intensified after redox cycle which increases the concentration of chemosorption centres. A conclusion is drawn that the method of SER spectroscopy of biomolecules adsorbed on "smooth" electrodes, permits obtaining information similar to that obtained from the analysis of Raman spectra of unadsorbed molecules, but at concentrations by two orders less. Adsorption on the electrodes treated with the help of redox cycle permits to obtain highly oriented preparations and to study topography of biopolymers in water solutions and suspensions.

  8. Influence of surface charge on the rate, extent, and structure of adsorbed Bovine Serum Albumin to gold electrodes.

    PubMed

    Beykal, Burcu; Herzberg, Moshe; Oren, Yoram; Mauter, Meagan S

    2015-12-15

    The objective of this work is to investigate the rate, extent, and structure of amphoteric proteins with charged solid surfaces over a range of applied potentials and surface charges. We use Electrochemical Quartz Crystal Microbalance with Dissipation Monitoring (E-QCM-D) to investigate the adsorption of amphoteric Bovine Serum Albumin (BSA) to a gold electrode while systematically varying the surface charge on the adsorbate and adsorbent by manipulating pH and applied potential, respectively. We also perform cyclic voltammetry-E-QCM-D on an adsorbed layer of BSA to elucidate conformational changes in response to varied applied potentials. We confirm previous results demonstrating that increasing magnitude of applied potential on the gold electrode is positively correlated with increasing mass adsorption when the protein and the surface are oppositely charged. On the other hand, we find that the rate of BSA adsorption is not governed by simple electrostatics, but instead depends on solution pH, an observation not well documented in the literature. Cyclic voltammetry with simultaneous E-QCM-D measurements suggest that BSA protein undergoes a conformational change as the surface potential varies.

  9. Evolution of Surface Motor Activation Zones in Hemiplegic Patients During 20 Sessions of FES Therapy with Multi-pad Electrodes

    PubMed Central

    Malešević, Jovana; Štrbac, Matija; Isaković, Milica; Kojić, Vladimir; Konstantinović, Ljubica; Vidaković, Aleksandra; Dedijer, Suzana; Kostić, Miloš; Keller, Thierry

    2016-01-01

    The purpose of this study was to examine surface motor activation zones for wrist, fingers and thumb extension movements and their temporal change during 20 therapy sessions using advanced multi-pad functional electrical stimulation system. Results from four hemiplegic patients indicate that certain zones have higher probability of eliciting each of the target movements. However, mutual overlap and variations of the zones are present not just between the subjects, but also on the intrasubject level, reflected through these session to session transformations of the selected virtual electrodes. The obtained results could be used as a priori knowledge for semi-automated optimization algorithm and could shorten the time required for calibration of the multi-pad electrode. PMID:27478575

  10. Methane conversion in surface- and volume-type dielectric barrier discharges generated in the presence of metal-mesh electrodes

    NASA Astrophysics Data System (ADS)

    Kobayashi, Kazunobu; Kulinich, S. A.; Ito, Tsuyohito

    2014-09-01

    Methane gas conversion was studied in customized flow-type reactors with different dielectric barrier discharge generated in Ar-CH4-O2 gas mixtures. Different reactor geometries (with either volume or surface-type discharges) and different electrode materials were compared, and gas temperatures during methane conversion processes were evaluated. The discharge was generated by applying either a conventional sinusoid or nanosecond-pulsed voltage. The methane conversion rate was as high as ˜99% with the total gas flow rate of 15 sccm, while the temperatures did not exceed 450 K. No significant effect of electrode material (stainless steel, aluminum, or CuO coated copper) was found, confirming that the conversion temperatures were much lower than those required for activity of typical catalysts. The reactor geometry, flow rate, and oxygen amount could be used to govern both the methane conversion rate and the fractions of components in the final product.

  11. Photoelectrochemical electrodes

    NASA Technical Reports Server (NTRS)

    Williams, R. M.; Rembaum, A. (Inventor)

    1983-01-01

    The surface of a moderate band gap semiconductor such as p-type molybdenum sulfide is modified to contain an adherent film of charge mediating ionene polymer containing an electroactive unit such as bipyridimium. Electron transport between the electrode and the mediator film is favorable and photocorrosion and recombination processes are suppressed. Incorporation of particles of catalyst such as platinum within the film provides a reduction in overvoltage. The polymer film is readily deposited on the electrode surface and can be rendered stable by ionic or addition crosslinking. Catalyst can be predispersed in the polymer film or a salt can be impregnated into the film and reduced therein.

  12. A Photo-ionization VOCs Sensor Developed the Resistance to Contamination of Electrode Surface

    NASA Astrophysics Data System (ADS)

    Hirano, Yasuyuki; Kazawa, Elito; Haramoto, Yoshiaki; Yoshida, Hiromichi

    A photo-ionization detector operated on alternating current using a lock-in amplifier was studied. Output current of covered electrodes with insulator was proportional to concentration of volatile organic compounds. And contamination made little effect on the current value.

  13. On optimal electrode configuration to estimate hand movements from forearm surface electromyography.

    PubMed

    Paleari, Marco; Di Girolamo, Michela; Celadon, Nicoló; Favetto, Alain; Ariano, Paolo

    2015-01-01

    Understanding the movement of the hand from sEMG signals acquired on the forearm is key in the development of future prosthetics of the upper limb. Despite the technical advancement on this technique, state of the art of sEMG still relies strongly on optimal electrode placement which is typically performed by a specialist by mean of a heuristic search. Involving a specialist has few major disadvantages including high costs and relatively long schedules. This work searches an optimal electrode configuration which could reduce or avoid the intervention of a specialist. More than 200 different possible electrode configurations were assessed by means of the average recognition rate over 11 different movements of the hand, wrist, and fingers. It is shown that using two rows of 8 equally spaced electrodes around the circumference of the forearm could be an optimal trade-off solution to accomplish the task of recognizing hand movement (ARR = 92%) without the need for a specialist or very complex hardware. PMID:26737680

  14. Guest-host complex formed between ascorbic acid and β-cyclodextrin immobilized on the surface of an electrode.

    PubMed

    Ramírez-Silva, María Teresa; Palomar-Pardavé, Manuel; Corona-Avendaño, Silvia; Romero-Romo, Mario; Alarcón-Angeles, Georgina

    2014-01-01

    This work deals with the formation of supramolecular complexes between ascorbic acid (AA), the guest, and β-cyclodextrin (β-CD), the host, that was first potentiodynamically immobilized on the surface of a carbon paste electrode (CPE) throughout the formation of a β-CD-based conducting polymer (poly-β-CD). With the bare CPE and the β-CD-modified CPE, an electrochemical study was performed to understand the effect of such surface modification on the electrochemical response of the AA. From this study it was shown that on the modified-CPE, the AA was surface-immobilized through formation of an inclusion complex with β-CD, which provoked the adsorption of AA in such a way that this stage became the limiting step for the electrochemical oxidation of AA. Moreover, from the analysis of the experimental voltammetric plots recorded during AA oxidation on the CPE/poly-β-CD electrode surfaces, the Gibbs' standard free energy of the inclusion complex formed by the oxidation product of AA and β-CD has been determined for the first time, ∆G0inclus = -36.4 kJ/mol. PMID:24818575

  15. Aquifer and Vadose Zone Pollution Determined From Geoelectrical Measurements With Multi- Electrode Wells and Surface Multi-Profiling

    NASA Astrophysics Data System (ADS)

    de Lima, O. A.; Pereira, P. D.

    2007-05-01

    During the last three years we are developing hydrobiogeological researches to quantitatively describe the underground contamination of a 4.0 km2 area, including two landfill deposits and a tannery industry of Alagoinhas city, Bahia state, Brazil. We used electrical geophysics, geological, geochemical and biological analysis to gain a general understanding of the complex interactions between organic and inorganic pollutants and their environmental impacts. A geological reconnaissance work and a geoelectrical survey using vertical electrical soundings were made around the area to detect and to delineate the extent of the underground contamination plume. The results pointed out the presence of a strong conductive anomaly within the aquifer resulting from invasive fluids both from the landfills and from the surface disposal lagoons from the tannery. Water samples collected at available wells and along the Sauipe river, have shown drastic changes in the total dissolved solids, total chromium, inorganic macro-components, biochemical oxygen demand, chemical oxygen demand, nutrients and bacterial content. As a complimentary work, apparent resistivity and chargeability data were measured as a function of depth along three new multi-electrode wells, and as a function of electrode spacing along five double semi-Schlumberger subsurface profiles. A multi-electrode well is a special monitoring well where we externally install copper electrodes as thin metallic rings spaced by 0.50 m, along its entire filter and casing length. Such electrodes are connected through insulated cables to the ground surface and may be combined into different arrays. Two-side semi-Schlumberger soundings expanded up to 200 m AB/2 spacing and with centers spaced by 50 m along special transverse centered at the plume were inverted using 1D and 2D models. Both techniques were used to detail the groundwater contamination around the Alagoinhas landfills. The electrical measurements performed at the earth

  16. Surface-induced intramolecular electron transfer in multi-centre redox metalloproteins: the di-haem protein cytochrome c4 in homogeneous solution and at electrochemical surfaces

    NASA Astrophysics Data System (ADS)

    Chi, Qijin; Zhang, Jingdong; Jensen, Palle S.; Nazmudtinov, Renat R.; Ulstrup, Jens

    2008-09-01

    Intramolecular electron transfer (ET) between transition metal centres is a core feature of biological ET and redox enzyme function. The number of microscopic redox potentials and ET rate constants is, however, mostly prohibitive for experimental mapping, but two-centre proteins offer simple enough communication networks for complete mapping to be within reach. At the same time, multi-centre redox proteins operate in a membrane environment where conformational dynamics and ET patterns are quite different from the conditions in a homogeneous solution. The bacterial respiratory di-haem protein Pseudomonas stutzeri cytochrome c4 offers a prototype target for environmental gating of intra-haem ET. ET between P. stutzeri cyt c4 and small molecular reaction partners in solution appears completely dominated by intermolecular ET of each haem group/protein domain, with no competing intra-haem ET, for which accompanying propionate-mediated proton transfer is a further barrier. The protein can, however, be immobilized on single-crystal, modified Au(111) electrode surfaces with either the low-potential N terminal or the high-potential C terminal domain facing the surface, clearly with fast intramolecular ET as a key feature in the electrochemical two-ET process. This dual behaviour suggests a pattern for multi-centre redox metalloprotein function. In a homogeneous solution, which is not the natural environment of cyt c4, the two haem group domains operate largely independently with conformations prohibitive for intramolecular ET. Binding to a membrane or electrochemical surface, however, triggers conformational opening of intramolecular ET channels. The haem group orientation in P. stutzeri cyt c4 is finally noted to offer a case for orientation dependent electronic rectification between a substrate and a tip in electrochemical in situ scanning tunnelling microscopy or nanoscale electrode configurations.

  17. Comparison of surface EMG signals between electrode types, interelectrode distances and electrode orientations in isometric exercise of the erector spinae muscle.

    PubMed

    Zedka, M; Kumar, S; Narayan, Y

    1997-10-01

    The influence of electrode type, interelectrode distance (IED) and electrode orientation on EMG signals from the paraspinal muscles was investigated. Bipolar electrodes were placed at distances 2, 3, 4, 6 and 8 cm over the erector spinae in the cranio-caudal direction ("in series") as well as in the direction perpendicular to it ("in parallel"). Ten subjects performed 5 s isometric contractions of the erector spinae at 20, 40, 60, 80 and 100% MVC by pulling upward on a handlebar attached to the floor. RMS EMG signals were analyzed for mean average amplitude (AA). Mean total power (TP) and mean median frequency (MF) of the raw EMG signal were determined using fast Fourier transform. In addition to graded loading, sustained fatiguing contractions were performed from which TP and MF were obtained. With increasing IED the AA and TP increased while MF decreased. Although a trend towards higher AA, TP and MF was found for electrodes "in series", as compared to those "in parallel", the difference never reached significance. It is concluded that consistent information about muscle activity was obtained with Miniature Biopotential Skin Electrodes and 14445C Hewlett-Packard electrodes independently from IED or orientation. Orientation "in parallel" prevented the electrodes from sliding during muscle contraction. The third tested type, electrodes developed in the Neuromuscular Research Center, Boston, proved extremely sensitive to movement.

  18. Effects of Nanowire Length and Surface Roughness on the Electrochemical Sensor Properties of Nafion-Free, Vertically Aligned Pt Nanowire Array Electrodes.

    PubMed

    Li, Zhiyang; Leung, Calvin; Gao, Fan; Gu, Zhiyong

    2015-01-01

    In this paper, vertically aligned Pt nanowire arrays (PtNWA) with different lengths and surface roughnesses were fabricated and their electrochemical performance toward hydrogen peroxide (H₂O₂) detection was studied. The nanowire arrays were synthesized by electroplating Pt in nanopores of anodic aluminum oxide (AAO) template. Different parameters, such as current density and deposition time, were precisely controlled to synthesize nanowires with different surface roughnesses and various lengths from 3 μm to 12 μm. The PtNWA electrodes showed better performance than the conventional electrodes modified by Pt nanowires randomly dispersed on the electrode surface. The results indicate that both the length and surface roughness can affect the sensing performance of vertically aligned Pt nanowire array electrodes. Generally, longer nanowires with rougher surfaces showed better electrochemical sensing performance. The 12 μm rough surface PtNWA presented the largest sensitivity (654 μA·mM⁻¹·cm⁻²) among all the nanowires studied, and showed a limit of detection of 2.4 μM. The 12 μm rough surface PtNWA electrode also showed good anti-interference property from chemicals that are typically present in the biological samples such as ascorbic, uric acid, citric acid, and glucose. The sensing performance in real samples (river water) was tested and good recovery was observed. These Nafion-free, vertically aligned Pt nanowires with surface roughness control show great promise as versatile electrochemical sensors and biosensors. PMID:26404303

  19. Effects of Nanowire Length and Surface Roughness on the Electrochemical Sensor Properties of Nafion-Free, Vertically Aligned Pt Nanowire Array Electrodes

    PubMed Central

    Li, Zhiyang; Leung, Calvin; Gao, Fan; Gu, Zhiyong

    2015-01-01

    In this paper, vertically aligned Pt nanowire arrays (PtNWA) with different lengths and surface roughnesses were fabricated and their electrochemical performance toward hydrogen peroxide (H2O2) detection was studied. The nanowire arrays were synthesized by electroplating Pt in nanopores of anodic aluminum oxide (AAO) template. Different parameters, such as current density and deposition time, were precisely controlled to synthesize nanowires with different surface roughnesses and various lengths from 3 μm to 12 μm. The PtNWA electrodes showed better performance than the conventional electrodes modified by Pt nanowires randomly dispersed on the electrode surface. The results indicate that both the length and surface roughness can affect the sensing performance of vertically aligned Pt nanowire array electrodes. Generally, longer nanowires with rougher surfaces showed better electrochemical sensing performance. The 12 μm rough surface PtNWA presented the largest sensitivity (654 μA·mM−1·cm−2) among all the nanowires studied, and showed a limit of detection of 2.4 μM. The 12 μm rough surface PtNWA electrode also showed good anti-interference property from chemicals that are typically present in the biological samples such as ascorbic, uric acid, citric acid, and glucose. The sensing performance in real samples (river water) was tested and good recovery was observed. These Nafion-free, vertically aligned Pt nanowires with surface roughness control show great promise as versatile electrochemical sensors and biosensors. PMID:26404303

  20. Fabrication of a nano-structured PbO2 electrode by using printing technology: Surface characterization and application

    NASA Astrophysics Data System (ADS)

    Kannan, K.; Muthuraman, G.; Cho, G.; Moon, I. S.

    2014-08-01

    This investigation aimed to introduce printing technology for the first time to prepare a nanostrucutured PbO2 electrode and its application to a cerium redox transfer process. The new method of nano-size PbO2 preparation demonstrated that nano-PbO2 could be obtained in less time and at less cost at room temperature. The prepared nano-PbO2 screen printed on a Ti electrode by three different compositions under similar conditions showed through surface and electrochemical analyses no adherence on Ti and no contact with other nano-PbO2 particles. Gravure printing of nano-PbO2 on a PET (poly ethylene thin) film at high pressure was done with two different compositions for the first time. The selective composition of 57.14 % nano-PbO2 powder with 4.28 % carbon black and 38.58 % ECA (ethyl carbitol acetate) produced a film with a nanoporous structure with an electron transfer ability. Finally, the optimized gravure-printed nano-PbO2 electrode was applied to the oxidation of Ce(III) to Ce(IV) by using cyclic voltammetry. The gravure-printed nano-PbO2 should pave the way to promising applications in electrochemical and sensor fields.

  1. Surface Activation of Electrocatalysis at Oxide Electrodes. Concerted Electron-Proton Transfer

    SciTech Connect

    Gagliardi, Christopher J.; Jurss, Jonah W.; Thorp, H. Holden; Meyer, Thomas J.

    2011-03-21

    Dramatic rate enhancements are observed for the oxidation of phenols, including tyrosine, at indium-tin oxide electrodes modified by the addition of the electron-transfer relays [MII(bpy)2(4,4'-(HO)2P(O)CH2)2bpy)]2+ (M = Ru, Os) with clear evidence for the importance of proton-coupled electron transfer and concerted electron-proton transfer.

  2. Surface-enhanced Raman scattering from crystal violet adsorbed on a silver electrode

    NASA Astrophysics Data System (ADS)

    Watanabe, Tadashi; Pettinger, Bruno

    1982-07-01

    SERS from crystal violet (CV) on a Ag electrode was investigated under preresonance and resonance conditions. The excitation profile of the chemisorbed species is like that of dissolved molecules but intensities are ≈ 1000 times larger. The Raman enhancement is ≈ 10 8 and exhibits a specific potential dependence even in the absence of adsorption-desorption process. At potentials where reduction of CV occurs leuco crystal violet was detected.

  3. Surface-initiated ring-opening metathesis polymerization of 5-(perfluorohexyl)norbornene on carbon paper electrodes.

    PubMed

    Faulkner, Christopher J; Payne, P Andrew; Jennings, G Kane

    2010-11-01

    Hydrophobic coatings on carbon paper electrodes are known to provide effective water management, superior gas transfer, and improved mechanical stability of the paper in fuel cell applications. Here, we describe the surface-initiated ring-opening metathesis polymerization (ROMP) of 5-(perfluorohexyl)norbornene (NBF6) to prepare fluorocarbon-rich films on carbon paper substrates that were pre-treated with O(2) plasma. For our reaction scheme, the growth of the pNBF6 films is dependent on the concentration of hydroxyl groups on the carbon paper substrate. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to determine the required time for O(2) plasma exposure to saturate the surface with hydroxyl-termini. Complete, conformal pNBF6 films were grown on carbon paper electrodes exposed to O(2) plasma for at least 45 s. These films exhibit hydrophobic and oleophobic surface properties and serve as insulative barriers to the diffusion of aqueous ions to the conductive carbon fibers. PMID:20709328

  4. Surface functionality and electrochemical investigations of a graphitic electrode as a candidate for alkaline energy conversion and storage devices

    PubMed Central

    Soliman, Ahmed B.; Abdel-Samad, Hesham S.; Abdel Rehim, Sayed S.; Hassan, Hamdy H.

    2016-01-01

    Graphite is a typical electrocatalyst support in alkaline energy conversion and storage devices such as fuel cells, supercapacitores and lithium ion batteries. The electrochemical behaviour of a graphite electrode in 0.5 M NaOH was studied to elucidate its surface structure/electrochemical activity relationship. Graphite voltammograms are characterized by an anodic shoulder AI and a cathodic peak CI in addition to the oxygen reduction reaction plateaus, PI and PII. AI and CI were attributed to oxidation and reduction of some graphite surface function groups, respectively. Rotating ring disk electrode (RRDE) study revealed two different oxygen types assigned as inner and outer oxygen. The inner oxygen was reduced via the more efficient 4-electron pathway. The outer oxygen reduction proceeded with a lower efficient 2-electron pathway. The calculated percentages of the 4-electron pathway were ranged from 70% to 90%. A full mechanism for the graphite surface function groups changes over the studied potential window was suggested through the combination between the voltammetric, FT-IR and Raman results. PMID:26916054

  5. A Combined “Electrochemical–Frustrated Lewis Pair” Approach to Hydrogen Activation: Surface Catalytic Effects at Platinum Electrodes

    PubMed Central

    Lawrence, Elliot J; Blagg, Robin J; Hughes, David L; Ashley, Andrew E; Wildgoose, Gregory G

    2015-01-01

    Herein, we extend our “combined electrochemical–frustrated Lewis pair” approach to include Pt electrode surfaces for the first time. We found that the voltammetric response of an electrochemical–frustrated Lewis pair (FLP) system involving the B(C6F5)3/[HB(C6F5)3]− redox couple exhibits a strong surface electrocatalytic effect at Pt electrodes. Using a combination of kinetic competition studies in the presence of a H atom scavenger, 6-bromohexene, and by changing the steric bulk of the Lewis acid borane catalyst from B(C6F5)3 to B(C6Cl5)3, the mechanism of electrochemical–FLP reactions on Pt surfaces was shown to be dominated by hydrogen-atom transfer (HAT) between Pt, [Pt–H] adatoms and transient [HB(C6F5)3]⋅ electrooxidation intermediates. These findings provide further insight into this new area of combining electrochemical and FLP reactions, and proffers additional avenues for exploration beyond energy generation, such as in electrosynthesis. PMID:25382457

  6. Surface functionality and electrochemical investigations of a graphitic electrode as a candidate for alkaline energy conversion and storage devices

    NASA Astrophysics Data System (ADS)

    Soliman, Ahmed B.; Abdel-Samad, Hesham S.; Abdel Rehim, Sayed S.; Hassan, Hamdy H.

    2016-02-01

    Graphite is a typical electrocatalyst support in alkaline energy conversion and storage devices such as fuel cells, supercapacitores and lithium ion batteries. The electrochemical behaviour of a graphite electrode in 0.5 M NaOH was studied to elucidate its surface structure/electrochemical activity relationship. Graphite voltammograms are characterized by an anodic shoulder AI and a cathodic peak CI in addition to the oxygen reduction reaction plateaus, PI and PII. AI and CI were attributed to oxidation and reduction of some graphite surface function groups, respectively. Rotating ring disk electrode (RRDE) study revealed two different oxygen types assigned as inner and outer oxygen. The inner oxygen was reduced via the more efficient 4-electron pathway. The outer oxygen reduction proceeded with a lower efficient 2-electron pathway. The calculated percentages of the 4-electron pathway were ranged from 70% to 90%. A full mechanism for the graphite surface function groups changes over the studied potential window was suggested through the combination between the voltammetric, FT-IR and Raman results.

  7. Surface functionality and electrochemical investigations of a graphitic electrode as a candidate for alkaline energy conversion and storage devices.

    PubMed

    Soliman, Ahmed B; Abdel-Samad, Hesham S; Abdel Rehim, Sayed S; Hassan, Hamdy H

    2016-01-01

    Graphite is a typical electrocatalyst support in alkaline energy conversion and storage devices such as fuel cells, supercapacitores and lithium ion batteries. The electrochemical behaviour of a graphite electrode in 0.5 M NaOH was studied to elucidate its surface structure/electrochemical activity relationship. Graphite voltammograms are characterized by an anodic shoulder AI and a cathodic peak CI in addition to the oxygen reduction reaction plateaus, PI and PII. AI and CI were attributed to oxidation and reduction of some graphite surface function groups, respectively. Rotating ring disk electrode (RRDE) study revealed two different oxygen types assigned as inner and outer oxygen. The inner oxygen was reduced via the more efficient 4-electron pathway. The outer oxygen reduction proceeded with a lower efficient 2-electron pathway. The calculated percentages of the 4-electron pathway were ranged from 70% to 90%. A full mechanism for the graphite surface function groups changes over the studied potential window was suggested through the combination between the voltammetric, FT-IR and Raman results. PMID:26916054

  8. Suppression of Photoanodic Surface Oxidation of n-Type 6H-SiC Electrodes in Aqueous Electrolytes.

    PubMed

    Sachsenhauser, Matthias; Walczak, Karl; Hampel, Paul A; Stutzmann, Martin; Sharp, Ian D; Garrido, Jose A

    2016-02-16

    The photoelectrochemical characterization of silicon carbide (SiC) electrodes is important for enabling a wide range of potential applications for this semiconductor. However, photocorrosion of the SiC surface remains a key challenge, because this process considerably hinders the deployment of this material into functional devices. In this report, we use cyclic voltammetry to investigate the stability of n-type 6H-SiC photoelectrodes in buffered aqueous electrolytes. For measurements in pure Tris buffer, photogenerated holes accumulate at the interface under anodic polarization, resulting in the formation of a porous surface oxide layer. Two possibilities are presented to significantly enhance the stability of the SiC photoelectrodes. In the first approach, redox molecules are added to the buffer solution to kinetically facilitate hole transfer to these molecules, and in the second approach, water oxidation in the electrolyte is induced by depositing a cobalt phosphate catalyst onto the semiconductor surface. Both methods are found to effectively suppress photocorrosion of the SiC electrodes, as confirmed by atomic force microscopy and X-ray photoelectron spectroscopy measurements. The presented study provides straightforward routes to stabilize n-type SiC photoelectrodes in aqueous electrolytes, which is essential for a possible utilization of this material in the fields of photocatalysis and multimodal biosensing. PMID:26795116

  9. Surface-initiated ring-opening metathesis polymerization of 5-(perfluorohexyl)norbornene on carbon paper electrodes.

    PubMed

    Faulkner, Christopher J; Payne, P Andrew; Jennings, G Kane

    2010-11-01

    Hydrophobic coatings on carbon paper electrodes are known to provide effective water management, superior gas transfer, and improved mechanical stability of the paper in fuel cell applications. Here, we describe the surface-initiated ring-opening metathesis polymerization (ROMP) of 5-(perfluorohexyl)norbornene (NBF6) to prepare fluorocarbon-rich films on carbon paper substrates that were pre-treated with O(2) plasma. For our reaction scheme, the growth of the pNBF6 films is dependent on the concentration of hydroxyl groups on the carbon paper substrate. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to determine the required time for O(2) plasma exposure to saturate the surface with hydroxyl-termini. Complete, conformal pNBF6 films were grown on carbon paper electrodes exposed to O(2) plasma for at least 45 s. These films exhibit hydrophobic and oleophobic surface properties and serve as insulative barriers to the diffusion of aqueous ions to the conductive carbon fibers.

  10. Corneal-shaping electrode

    DOEpatents

    Doss, James D.; Hutson, Richard L.

    1982-01-01

    The disclosure relates to a circulating saline electrode for changing corneal shape in eyes. The electrode comprises a tubular nonconductive electrode housing having an annular expanded base which has a surface substantially matched to a subject corneal surface. A tubular conductive electrode connected to a radiofrequency generating source is disposed within the electrode housing and longitudinally aligned therewith. The electrode has a generally hemispherical head having at least one orifice. Saline solution is circulated through the apparatus and over the cornea to cool the corneal surface while radiofrequency electric current emitted from the electrode flows therefrom through the cornea to a second electrode, on the rear of the head. This current heats the deep corneal stroma and thereby effects corneal reshaping as a biological response to the heat.

  11. Surface potential measurement of fullerene derivative/copper phthalocyanine on indium tin oxide electrode by Kelvin probe force microscopy

    NASA Astrophysics Data System (ADS)

    Satoh, Nobuo; Yamaki, Michio; Noda, Kei; Katori, Shigetaka; Kobayashi, Kei; Matsushige, Kazumi; Yamada, Hirofumi

    2015-08-01

    We have investigated the organic semiconductor thin films deposited by vacuum evaporation deposition using intersecting metal shadow masks on indium tin oxide (ITO) electrode/glass substrates to simulate organic solar cells by simultaneous observation with dynamic force microscopy (DFM)/Kelvin-probe force microscopy (KFM). The energy band diagram was depicted by simultaneously obtaining topographic and surface potential images of the same area using DFM/KFM. We considered the charge behavior at the interface having band bending in the phenyl-C61-butyric acid methyl ester (PCBM) film.

  12. Formation of macroscopic surface layers on Fe(0) electrocoagulation electrodes during an extended field trial of arsenic treatment.

    PubMed

    van Genuchten, Case M; Bandaru, Siva R S; Surorova, Elena; Amrose, Susan E; Gadgil, Ashok J; Peña, Jasquelin

    2016-06-01

    Extended field trials to remove arsenic (As) via Fe(0) electrocoagulation (EC) have demonstrated consistent As removal from groundwater to concentrations below 10 μg L(-1). However, the coulombic performance of long-term EC field operation is lower than that of laboratory-based systems. Although EC electrodes used over prolonged periods show distinct passivation layers, which have been linked to decreased treatment efficiency, the spatial distribution and mineralogy of such surface layers have not been investigated. In this work, we combine wet chemical measurements with sub-micron-scale chemical maps and selected area electron diffraction (SAED) to determine the chemical composition and mineral phase of surface layers formed during long-term Fe(0) EC treatment. We analyzed Fe(0) EC electrodes used for 3.5 months of daily treatment of As-contaminated groundwater in rural West Bengal, India. We found that the several mm thick layer that formed on cathodes and anodes consisted of primarily magnetite, with minor fractions of goethite. Spatially-resolved SAED patterns also revealed small quantities of CaCO3, Mn oxides, and SiO2, the source of which was the groundwater electrolyte. We propose that the formation of the surface layer contributes to decreased treatment performance by preventing the migration of EC-generated Fe(II) to the bulk electrolyte, where As removal occurs. The trapped Fe(II) subsequently increases the surface layer size at the expense of treatment efficiency. Based on these findings, we discuss several simple and affordable methods to prevent the efficiency loss due to the surface layer, including alternating polarity cycles and cleaning the Fe(0) surface mechanically or via electrolyte scouring. PMID:27018519

  13. Formation of macroscopic surface layers on Fe(0) electrocoagulation electrodes during an extended field trial of arsenic treatment.

    PubMed

    van Genuchten, Case M; Bandaru, Siva R S; Surorova, Elena; Amrose, Susan E; Gadgil, Ashok J; Peña, Jasquelin

    2016-06-01

    Extended field trials to remove arsenic (As) via Fe(0) electrocoagulation (EC) have demonstrated consistent As removal from groundwater to concentrations below 10 μg L(-1). However, the coulombic performance of long-term EC field operation is lower than that of laboratory-based systems. Although EC electrodes used over prolonged periods show distinct passivation layers, which have been linked to decreased treatment efficiency, the spatial distribution and mineralogy of such surface layers have not been investigated. In this work, we combine wet chemical measurements with sub-micron-scale chemical maps and selected area electron diffraction (SAED) to determine the chemical composition and mineral phase of surface layers formed during long-term Fe(0) EC treatment. We analyzed Fe(0) EC electrodes used for 3.5 months of daily treatment of As-contaminated groundwater in rural West Bengal, India. We found that the several mm thick layer that formed on cathodes and anodes consisted of primarily magnetite, with minor fractions of goethite. Spatially-resolved SAED patterns also revealed small quantities of CaCO3, Mn oxides, and SiO2, the source of which was the groundwater electrolyte. We propose that the formation of the surface layer contributes to decreased treatment performance by preventing the migration of EC-generated Fe(II) to the bulk electrolyte, where As removal occurs. The trapped Fe(II) subsequently increases the surface layer size at the expense of treatment efficiency. Based on these findings, we discuss several simple and affordable methods to prevent the efficiency loss due to the surface layer, including alternating polarity cycles and cleaning the Fe(0) surface mechanically or via electrolyte scouring.

  14. Experimental and Theoretical Studies on Oxidation of Cu-Au Alloy Surfaces: Effect of Bulk Au Concentration.

    PubMed

    Okada, Michio; Tsuda, Yasutaka; Oka, Kohei; Kojima, Kazuki; Diño, Wilson Agerico; Yoshigoe, Akitaka; Kasai, Hideaki

    2016-01-01

    We report results of our experimental and theoretical studies on the oxidation of Cu-Au alloy surfaces, viz., Cu3Au(111), CuAu(111), and Au3Cu(111), using hyperthermal O2 molecular beam (HOMB). We observed strong Au segregation to the top layer of the corresponding clean (111) surfaces. This forms a protective layer that hinders further oxidation into the bulk. The higher the concentration of Au in the protective layer formed, the higher the protective efficacy. As a result, of the three Cu-Au surfaces studied, Au3Cu(111) is the most stable against dissociative adsorption of O2, even with HOMB. We also found that this protective property breaks down for oxidations occurring at temperatures above 300 K. PMID:27516137

  15. Experimental and Theoretical Studies on Oxidation of Cu-Au Alloy Surfaces: Effect of Bulk Au Concentration

    PubMed Central

    Okada, Michio; Tsuda, Yasutaka; Oka, Kohei; Kojima, Kazuki; Diño, Wilson Agerico; Yoshigoe, Akitaka; Kasai, Hideaki

    2016-01-01

    We report results of our experimental and theoretical studies on the oxidation of Cu-Au alloy surfaces, viz., Cu3Au(111), CuAu(111), and Au3Cu(111), using hyperthermal O2 molecular beam (HOMB). We observed strong Au segregation to the top layer of the corresponding clean (111) surfaces. This forms a protective layer that hinders further oxidation into the bulk. The higher the concentration of Au in the protective layer formed, the higher the protective efficacy. As a result, of the three Cu-Au surfaces studied, Au3Cu(111) is the most stable against dissociative adsorption of O2, even with HOMB. We also found that this protective property breaks down for oxidations occurring at temperatures above 300 K. PMID:27516137

  16. Towards combined electrochemistry and surface-enhanced resonance Raman of heme proteins: Improvement of diffusion electrochemistry of cytochrome c at silver electrodes chemically modified with 4-mercaptopyridine.

    PubMed

    Millo, Diego; Ranieri, Antonio; Koot, Wynanda; Gooijer, Cees; van der Zwan, Gert

    2006-08-01

    To date, a successful combination of surface-enhanced resonance Raman spectroscopy (SERRS) and electrochemistry to study heme proteins is inhibited by the problems raised by the prerequisite to use silver as electrode metal. This paper indicates an approach to overcome these problems. It describes a quick and reproducible procedure to prepare silver electrodes chemically modified with 4-mercaptopyridine suitable to perform diffusion electrochemistry of cytochrome c (cyt c). The method involves the employment of a mechanical and a chemical treatment and avoids the use of alumina slurries and any electrochemical pretreatment. Cyclic voltammetry (CV) was used to test the electrochemical response of cyt c, and the CV signals were found identical with those obtained on gold electrodes under the same experimental conditions. Compared to previous literature, a significant improvement of the CV signal of cyt c at silver electrodes was achieved. Preliminary results show that this treatment can be also successfully employed for the preparation of SERRS-active electrodes.

  17. Electrochemical, interfacial, and surface studies of the conversion of carbon dioxide to liquid fuels on tin electrodes

    NASA Astrophysics Data System (ADS)

    Wu, Jingjie

    maximize the triple phase boundary length for simultaneous high current density and selectivity towards formate formation (Chapter 3). The Sn GDEs was incorporated into a home-designed scalable full electrochemical cell which features a buffer layer of circulating liquid electrolyte mediating the proton concentration at cathode electrode surface. The Sn GDEs exhibited excellent short-term performance for CO2 reduction with high selectivity towards formate formation at low overpotentials in the full electrochemical cell. Additionally, coupling water oxidation and CO2 reduction was demonstrated in this full electrochemical cell to mimic biosynthesis (Chapter 4). The rapid degradation of selectivity towards formate formation on Sn GDEs in the full electrochemical cell, however, was observed during long-term operation. The degradation mechanism was unraveled due to the decrease of electrode potential resulted from substantial increase of internal ohmic resistance of the full electrochemical cell. The unexpected rise of internal ohmic resistance was attributed to the pulverization of 100 nm Sn nanoparticles due to the hydrogen diffusion induced stress. Based on the understanding of the origin of Sn nanoparticles pulverization, SnO2 nanoparticles of 3˜3.5 nm close to the critical size were utilized and reduced in situ to form Sn catalyst for electrochemical reduction of CO2. The pulverization was suppressed and subsequently a stable performance of electrodes was obtained (Chapter 5). Due to the affinity to oxygen, Sn nanoparticle surface is covered by a native thin oxide layer. The performance of Sn GDEs towards CO2 reduction strongly depends on the initial thickness of the surface oxide layer. The selectivity towards formate production dropped while the hydrogen yield increased as the initial thickness of the oxide layer increased (Chapter 6). These results suggest the underlying of surface structure on the selectivity of Sn electrode for CO2 reduction and provide insight into

  18. Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode

    DOE PAGES

    Cui, Chaonan; Han, Jinyu; Zhu, Xinli; Liu, Xiao; Wang, Hua; Mei, Donghai; Ge, Qingfeng

    2016-01-16

    In this study, tin oxide (SnOx) formation on tin-based electrode surfaces during CO2 electrochemical reduction can have a significant impact on the activity and selectivity of the reaction. In the present study, density functional theory (DFT) calculations have been performed to understand the role of SnOx in CO2 reduction using a SnO monolayer on the Sn(112) surface as a model for SnOx. Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H2O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface. CO2 energetically prefers to react withmore » the hydroxyl, forming a bicarbonate (HCO3(t)*) intermediate, which can then be reduced to either formate (HCOO*) by hydrogenating the carbon atom or carboxyl (COOH*) by protonating the oxygen atom. Both steps involve a simultaneous Csingle bondO bond breaking. Further reduction of HCOO* species leads to the formation of formic acid in the acidic solution at pH < 4, while the COOH* will decompose to CO and H2O via protonation. Whereas the oxygen vacancy (VO) in the oxide monolayer maybe formed by the reduction, it can be recovered by H2O dissociation, resulting in two embedded hydroxyl groups. The results show that the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO2 reduction than the hydroxylated VO surface with two embedded hydroxyls. The reduction potential for the former has a limiting-potential of –0.20 V (RHE), lower than that for the latter (–0.74 V (RHE)). Compared to the pure Sn electrode, the formation of SnOx monolayer on the electrode under the operating conditions promotes CO2 reduction more effectively by forming surface hydroxyls, thereby providing a new channel via COOH* to the CO formation, although formic acid is still the major reduction product.« less

  19. Sixty-four channel wearable acquisition system for long-term surface electromyogram recording with electrode arrays.

    PubMed

    Pozzo, M; Bottin, A; Ferrabone, R; Merletti, R

    2004-07-01

    The use of mono- and bi-dimensional electromyogram (EMG) electrode arrays for the assessment of the neuromuscular system can provide an insight into muscle physiology not achieved with classical bipolar surface EMG. Among the advantages of multichannel EMG detection, there is a) the possibility of estimating muscle fibre conduction velocity, even during motor tasks, and b) the possibility to increase the number of detection points on a muscle, improving the performance of pattern-based EMG decomposition methods. For these reasons, the development and use of multichannel surface EMG devices and techniques were chosen as the primary goals within the European RTD Project 'Neuromuscular assessment in the elderly worker' (NEW). The specific requirements of Project NEW called for the availability of a user-friendly, small-sized EMG acquisition system for field use, suitable for multichannel EMG recording using electrode arrays from one or more muscles. A market survey established that none of the commercially available EMG acquisition systems featured all the desired specifications, nor could they be easily adapted for specific use. The paper describes the design of an innovative acquisition system for long-term multichannel EMG recording fulfilling these requirements and comprising adhesive electrode arrays for artifact-free EMG acquisition during work activity and a portable, user-friendly, battery-powered acquisition system for multichannel EMG recording and storage on a removable PCMCIA card. The system has been used extensively within Project NEW for laboratory and field tests and can find applications in other fields of basic and applied research, including ergonomics, occupational and sports medicine.

  20. Charge trapping induced by plasma in alumina electrode surface investigated by thermoluminescence and optically stimulated luminescence

    SciTech Connect

    Ambrico, P. F.; Ambrico, M.; Schiavulli, L.; Ligonzo, T.; Augelli, V.

    2009-02-02

    The plasma of a dielectric barrier discharge can fill traps in the alumina that cover the electrode. Trap energies and lifetimes are estimated by thermoluminescence and optically stimulated luminescence. Comparison with similar results for traps created by other radiation sources clarifies the mechanisms regulating this effect. Alumina's trap energies are approximately 1 eV, and the traps remain active for several days after plasma exposure. These results could be important to keep dielectric barrier discharge plasmas uniform since a trapped charge can be an electron reservoir.

  1. High performance cermet electrodes

    DOEpatents

    Isenberg, Arnold O.; Zymboly, Gregory E.

    1986-01-01

    Disclosed is a method of increasing the operating cell voltage of a solid oxide electrochemical cell having metal electrode particles in contact with an oxygen-transporting ceramic electrolyte. The metal electrode is heated with the cell, and oxygen is passed through the oxygen-transporting ceramic electrolyte to the surface of the metal electrode particles so that the metal electrode particles are oxidized to form a metal oxide layer between the metal electrode particles and the electrolyte. The metal oxide layer is then reduced to form porous metal between the metal electrode particles and the ceramic electrolyte.

  2. Role of surface oxides in the formation of solid-electrolyte interphases at silicon electrodes for lithium-ion batteries.

    PubMed

    Schroder, Kjell W; Dylla, Anthony G; Harris, Stephen J; Webb, Lauren J; Stevenson, Keith J

    2014-12-10

    Nonaqueous solvents in modern battery technologies undergo electroreduction at negative electrodes, leading to the formation of a solid-electrolyte interphase (SEI). The mechanisms and reactions leading to a stable SEI on silicon electrodes in lithium-ion batteries are still poorly understood. This lack of understanding inhibits the rational design of electrolyte additives, active material coatings, and the prediction of Li-ion battery life in general. We prepared SEI with a common nonaqueous solvent (LiPF6 in PC and in EC/DEC 1:1 by wt %) on silicon oxide and etched silicon (001) surfaces in various states of lithiation to understand the role of surface chemistry on the SEI formation mechanism and SEI structure. Anhydrous and anoxic techniques were used to prevent air and moisture contamination of prepared SEI films, allowing for more accurate characterization of SEI chemical stratification and composition by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) depth profiling. Additionally, multivariate statistical methods were used to better understand TOF-SIMS depth profiling studies. We conclude that the absence of native-oxide layer on silicon has a significant impact on the formation, composition, structure, and thickness of the SEI. PMID:25402271

  3. Thermodynamic properties of hydrogen-water adsorption at terraces and steps of Pt(111) vicinal surface electrodes

    NASA Astrophysics Data System (ADS)

    Gómez-Marín, Ana M.; Feliu, Juan M.

    2016-04-01

    In this work, the effect of temperature on the adsorption states of Pt(111) vicinal surface electrodes in perchloric acid is studied through a thermodynamic analysis. The method allows calculating thermodynamic properties of the interface. In this framework, the concept of the generalized isotherm and the statistical thermodynamics description are applied to calculate formal entropies, enthalpies and Gibbs energies, ΔGbari0, of the adsorption processes at two-dimensional terraces and one-dimensional steps. These values are compared with data from literature. Additionally, the effect of the step density on ΔGbari0 and on the lateral interactions between adsorbed species, ωij, at terraces and steps is also determined. Calculated ΔGbari0, entropies and enthalpies are almost temperature-independent, especially at steps, but they depend on the step orientation. In contrast, ΔGbari0 and ωij at terraces depend on the step density, following a linear tendency for terrace lengths larger than 5 atoms. However, while ΔGbari0 increases with the step density, ωij decreases. Results were explained by considering the modification in the energetic surface balance by hydrogen, Hads, and water, H2Oads, co-adsorption on the electrode, which in turn determines the whole adsorption processes on terraces and steps.

  4. Surface loss probability of atomic hydrogen for different electrode cover materials investigated in H₂-Ar low-pressure plasmas

    SciTech Connect

    Sode, M. Schwarz-Selinger, T.; Jacob, W.; Kersten, H.

    2014-07-07

    In an inductively coupled H₂-Ar plasma at a total pressure of 1.5 Pa, the influence of the electrode cover material on selected line intensities of H, H₂, and Ar are determined by optical emission spectroscopy and actinometry for the electrode cover materials stainless steel, copper, tungsten, Macor{sup ®}, and aluminum. Hydrogen dissociation degrees for the considered conditions are determined experimentally from the measured emission intensity ratios. The surface loss probability β{sub H} of atomic hydrogen is correlated with the measured line intensities, and β{sub H} values are determined for the considered materials. Without the knowledge of the atomic hydrogen temperature, β{sub H} cannot be determined exactly. However, ratios of β{sub H} values for different surface materials are in first order approximation independent of the atomic hydrogen temperature. Our results show that β{sub H} of copper is equal to the value of stainless steel, β{sub H} of Macor{sup ®} and tungsten is about 2 times smaller and β{sub H} of aluminum about 5 times smaller compared with stainless steel. The latter ratio is in reasonable agreement with literature. The influence of the atomic hydrogen temperature T{sub H} on the absolute value is thoroughly discussed. For our assumption of T{sub H}=600 K, we determine a β{sub H} for stainless steel of 0.39±0.13.

  5. Flexible transparent conducting hybrid film using a surface-embedded copper nanowire network: a highly oxidation-resistant copper nanowire electrode for flexible optoelectronics.

    PubMed

    Im, Hyeon-Gyun; Jung, Soo-Ho; Jin, Jungho; Lee, Dasom; Lee, Jaemin; Lee, Daewon; Lee, Jung-Yong; Kim, Il-Doo; Bae, Byeong-Soo

    2014-10-28

    We report a flexible high-performance conducting film using an embedded copper nanowire transparent conducting electrode; this material can be used as a transparent electrode platform for typical flexible optoelectronic devices. The monolithic composite structure of our transparent conducting film enables simultaneously an outstanding oxidation stability of the copper nanowire network (14 d at 80 °C), an exceptionally smooth surface topography (R(rms) < 2 nm), and an excellent opto-electrical performances (Rsh = 25 Ω sq(-1) and T = 82%). A flexible organic light emitting diode device is fabricated on the transparent conducting film to demonstrate its potential as a flexible copper nanowire electrode platform.

  6. Fuel cell electrodes

    SciTech Connect

    Strmcnik, Dusan; Cuesta, Angel; Stamenkovic, Vojislav; Markovic, Nenad

    2015-06-23

    A process includes patterning a surface of a platinum group metal-based electrode by contacting the electrode with an adsorbate to form a patterned platinum group metal-based electrode including platinum group metal sites blocked with adsorbate molecules and platinum group metal sites which are not blocked.

  7. High frequency reference electrode

    DOEpatents

    Kronberg, James W.

    1994-01-01

    A high frequency reference electrode for electrochemical experiments comprises a mercury-calomel or silver-silver chloride reference electrode with a layer of platinum around it and a layer of a chemically and electrically resistant material such as TEFLON around the platinum covering all but a small ring or "halo" at the tip of the reference electrode, adjacent to the active portion of the reference electrode. The voltage output of the platinum layer, which serves as a redox electrode, and that of the reference electrode are coupled by a capacitor or a set of capacitors and the coupled output transmitted to a standard laboratory potentiostat. The platinum may be applied by thermal decomposition to the surface of the reference electrode. The electrode provides superior high-frequency response over conventional electrodes.

  8. High frequency reference electrode

    DOEpatents

    Kronberg, J.W.

    1994-05-31

    A high frequency reference electrode for electrochemical experiments comprises a mercury-calomel or silver-silver chloride reference electrode with a layer of platinum around it and a layer of a chemically and electrically resistant material such as TEFLON around the platinum covering all but a small ring or halo' at the tip of the reference electrode, adjacent to the active portion of the reference electrode. The voltage output of the platinum layer, which serves as a redox electrode, and that of the reference electrode are coupled by a capacitor or a set of capacitors and the coupled output transmitted to a standard laboratory potentiostat. The platinum may be applied by thermal decomposition to the surface of the reference electrode. The electrode provides superior high-frequency response over conventional electrodes. 4 figs.

  9. Micromachined electrode array

    DOEpatents

    Okandan, Murat; Wessendorf, Kurt O.

    2007-12-11

    An electrode array is disclosed which has applications for neural stimulation and sensing. The electrode array, in certain embodiments, can include a plurality of electrodes each of which is flexibly attached to a common substrate using a plurality of springs to allow the electrodes to move independently. In other embodiments of the electrode array, the electrodes can be fixed to the substrate. The electrode array can be formed from a combination of bulk and surface micromachining, and can include electrode tips having an electroplated metal (e.g. platinum, iridium, gold or titanium) or a metal oxide (e.g. iridium oxide) for biocompatibility. The electrode array can be used to form a part of a neural prosthesis, and is particularly well adapted for use in an implantable retinal prosthesis.

  10. Flexible retinal electrode array

    DOEpatents

    Okandan, Murat; Wessendorf, Kurt O.; Christenson, Todd R.

    2006-10-24

    An electrode array which has applications for neural stimulation and sensing. The electrode array can include a large number of electrodes each of which is flexibly attached to a common substrate using a plurality of springs to allow the electrodes to move independently. The electrode array can be formed from a combination of bulk and surface micromachining, with electrode tips that can include an electroplated metal (e.g. platinum, iridium, gold or titanium) or a metal oxide (e.g. iridium oxide) for biocompatibility. The electrode array can be used to form a part of a neural prosthesis, and is particularly well adapted for use in an implantable retinal prosthesis where the electrodes can be tailored to provide a uniform gentle contact pressure with optional sensing of this contact pressure at one or more of the electrodes.

  11. Formation of Nanocrystalline Surface of Cu-Sn Alloy Foam Electrochemically Produced for Li-Ion Battery Electrode.

    PubMed

    Ye, Bora; Kim, Sunjung

    2015-10-01

    Cu-Sn alloy foam is a promising electrode material for Li-ion batteries. In this study, Cu-Sn alloy foam was produced by diffusion-limited electrodeposition in alkaline electrolyte using polyurethane (PU) foam template. Our major concern is to form Cu-Sn alloy foam with nanocrystalline surface morphology by adjusting electrodeposition conditions such as deposition potential and metal ion concentration. Cu-Sn alloy layers comprising of nanoclusters such as nanospheres, nanoellipsoids, and nanoflakes were created depending on electrodeposition conditions. Larger surface area of nanocluster-interconnected Cu-Sn alloy layer was created when both Sn concentration and negative deposition potential were higher. After decomposing PU template thermally, Cu-Sn alloy foam of Cu, Cu6Sn5, and Cu3Sn phases was finally produced. PMID:26726491

  12. Use of Refractory Nanoparticles as a Component of Welding Materials in Welding and Surfacing With Coated Electrodes and Flux Cored Wires

    NASA Astrophysics Data System (ADS)

    Kartsev, D. S.; Zernin, E. A.

    2016-08-01

    The authors address to the issue of mainstream directions and application fields of nanostructured coated electrodes and flux cored wires, their distinctive advantages and shortcomings. Some consideration is given to use of refractory nanoparticles and their influence on the structure and properties of metal when welding and surfacing with flux cored wires and coated electrodes. The results of research carried out in this sphere are analyzed.

  13. Magnetohydrodynamic electrode

    DOEpatents

    Marchant, David D.; Killpatrick, Don H.

    1978-01-01

    An electrode capable of withstanding high temperatures and suitable for use as a current collector in the channel of a magnetohydrodynamic (MHD) generator consists of a sintered powdered metal base portion, the upper surface of the base being coated with a first layer of nickel aluminide, an intermediate layer of a mixture of nickel aluminide - refractory ceramic on the first layer and a third or outer layer of a refractory ceramic material on the intermediate layer. The sintered powdered metal base resists spalling by the ceramic coatings and permits greater electrode compliance to thermal shock. The density of the powdered metal base can be varied to allow optimization of the thermal conductivity of the electrode and prevent excess heat loss from the channel.

  14. Surface plasmon enhanced Raman scattering frequency and angular resonance of Raman scattered light from pyridine on Au, Ag and Cu electrodes

    NASA Astrophysics Data System (ADS)

    Pettinger, B.; Wenning, U.; Wetzel, H.

    1980-12-01

    The strong dependence of the surface Raman intensity on the exciting frequency and on the angle of incidence for pyridine molecules adsorbed on Au, Ag and Cu electrodes after a weak oxidation/reduction cycle is evidence for a surface plasmon enhanced Raman scattering (SPERS).

  15. Monte Carlo study of molten salt with charge asymmetry near the electrode surface

    NASA Astrophysics Data System (ADS)

    Kłos, Jacek; Lamperski, Stanisław

    2014-02-01

    Results of the Monte Carlo simulation of the electrode | molten salt or ionic liquid interface are reported. The system investigated is approximated by the primitive model of electrolyte being in contact with a charged hard wall. Ions differ in charges, namely anions are divalent and cations are monovalent but they are of the same diameter d = 400 pm. The temperature analysis of heat capacity at a constant volume Cv and the anion radial distribution function, g2-/2-, allowed the choice of temperature of the study, which is T = 2800 K and corresponds to T* = 0.34 (definition of reduced temperature T* in text). The differential capacitance curve of the interface with the molten salt or ionic liquid at c = 5.79 M has a distorted bell shape. It is shown that with increasing electrolyte concentration from c = 0.4 to 5 M the differential capacitance curves undergo transition from U shape to bell shape.

  16. Monte Carlo study of molten salt with charge asymmetry near the electrode surface.

    PubMed

    Kłos, Jacek; Lamperski, Stanisław

    2014-02-01

    Results of the Monte Carlo simulation of the electrode | molten salt or ionic liquid interface are reported. The system investigated is approximated by the primitive model of electrolyte being in contact with a charged hard wall. Ions differ in charges, namely anions are divalent and cations are monovalent but they are of the same diameter d = 400 pm. The temperature analysis of heat capacity at a constant volume Cv and the anion radial distribution function, g2-/2-, allowed the choice of temperature of the study, which is T = 2800 K and corresponds to T(*) = 0.34 (definition of reduced temperature T(*) in text). The differential capacitance curve of the interface with the molten salt or ionic liquid at c = 5.79 M has a distorted bell shape. It is shown that with increasing electrolyte concentration from c = 0.4 to 5 M the differential capacitance curves undergo transition from U shape to bell shape.

  17. Electroanalysis using macro-, micro-, and nanochemical architectures on electrode surfaces. Bulk surface modification of glassy carbon microspheres with gold nanoparticles and their electrical wiring using carbon nanotubes.

    PubMed

    Dai, Xuan; Wildgoose, Gregory G; Salter, Chris; Crossley, Alison; Compton, Richard G

    2006-09-01

    Gold nanoparticles (approximately 30-60 nm in diameter) were deposited onto the surface of glassy carbon microspheres (10-20 microm) through electroless plating to produce bulk (i.e., gram) quantities of nanoparticle surface-modified microspheres. The gold nanoparticle-modified powder was then characterized by means of scanning electron microscopy and cyclic voltammetry. The voltammetric response of a macroelectrode consisting of a film of gold nanoparticle-modified glassy carbon microspheres, bound together and "wired-up" using multiwalled carbon nanotubes (MWCNTs), was investigated. We demonstrate that by intelligently exploiting both nano- and microchemical architectures and wiring up the electroactive centers using MWCNTs in this way, we can obtain macroelectrode voltammetric behavior while only using approximately 1% by mass of the expensive gold material that would be required to construct the equivalent gold film macrodisk electrode. The potential utility of electrodes constructed using chemical architectures such as this was demonstrated by applying them to the analytical determination of arsenic(III) concentration. An optimized limit of detection of 2.5 ppb was obtained.

  18. Temperature dependence of proton electroreduction kinetics at gold(111) and (210) surfaces

    NASA Astrophysics Data System (ADS)

    Hamelin, A.; Stoicoviciu, L.; Chang, S. C.; Weaver, M. J.

    1991-05-01

    Rate-potential data are reported for proton electroreduction on Au(111) and (210) in acidic perchlorate electrolytes over the temperature range 0 to 60 C, and examined with regard to temperature dependence of the transfer coefficient alpha. Since the Tafel plots exhibit significant curvature the analysis requires information on the temperature-dependent thermodynamics (i.e., the reaction entropy) for the proton discharge step. This was estimated from temperature-dependent voltammetry of reversible proton discharge to form adsorbed hydrogen on platinum. When evaluated at a constant overpotential for the proton discharge step, alpha for this reaction on both Au(111) and (210) is independent of temperature. An effect of electrocatalysts for proton reduction on Au(111) engendered by prior voltametric oxide formation was also observed. This effect is attributed to formation of surface defects on the basis of recently reported scanning tunneling microscopy data. Surface structural changes are also evident in the morphology of cyclic voltammograms obtained in the double-layer region. Electrochemical effects disappear with time when potential is held in the double layer region, and more rapidly at higher temperatures.

  19. Faradaic phase transition of dibenzyl viologen on an HOPG electrode surface studied by in situ electrochemical STM and electroreflectance spectroscopy.

    PubMed

    Higashi, Tomohiro; Shigemitsu, Yasuhiro; Sagara, Takamasa

    2011-11-15

    Phase transitions of an adsorption layer of dibenzyl viologen (dBV) as a typical diaryl viologen on a basal plane of a highly oriented pyrolytic graphite (HOPG) electrode are described using voltammetry, in situ electrochemical scanning tunneling microscopy (EC-STM), and electroreflectance (ER) spectroscopy. A monolayer redox process at less negative potential than the bulk redox process was found to be the first-order faradaic phase transition between a gaslike adsorption layer of dication (dBV(2+)) and a 2D condensed monolayer of radical cation (dBV(•+)). Comparison of the results of cyclic voltammetry and potential step chronoamperometry was made with those of heptyl viologen (HV), which also undergoes a faradaic phase transition of the first order. It suggested that the contribution of intermolecular π-π interaction between benzyl groups of dBV to the phase transition is minor and apparently equivalent to interchain interaction between the heptyl chains of HV. In situ EC-STM images of the 2D condensed monolayer demonstrated stripe patterns of the rows of dBV(•+) molecules forming 3-fold rotationally symmetric domains. The results of the ER measurements also revealed that the orientation of the longitudinal molecular axis of the bipyridinium moiety of dBV(•+) molecules lying flat on the HOPG electrode surface, most likely with a side-on configuration.

  20. The role of Cu atoms on silver electrodes in surface enhanced Raman scattering from pyridine: Giant enhancement by a minority of adsorbed molecules

    NASA Astrophysics Data System (ADS)

    Moerl, Ludwig; Pettinger, Bruno

    1982-08-01

    Surface enhanced Raman scattering (SERS) has been studied for pyridine molecules adsorbed at Ag electrodes covered with submonolayers of Cu ( θ = 0.003 - 0.1). Depending on the amount of Cu coverage the frequencies of the breathing vibrations shift, and new breathing modes appear. Obviously two types of pyridine complexes are formed, differing in the nature of the bonding provided either by copper or silver surface atoms. The generation and quenching behaviour of SERS at rough electrodes evidence the importance of metastable atomic surface structures for SERS and indicate the cooperation of local and non-local enhancement processes. Since active sites can be stabilized with traces of Cu at the silver electrode, the enhancement factor on a molecular basis appears to be by one order of magnitude larger than earlier anticipated, and ranges from 2 × 10 6 to 1.6 × 10 7 for an exciting wavelength at 514.5 nm or 647.1 nm, respectively.

  1. Error compensation of single-qubit gates in a surface-electrode ion trap using composite pulses

    NASA Astrophysics Data System (ADS)

    Mount, Emily; Kabytayev, Chingiz; Crain, Stephen; Harper, Robin; Baek, So-Young; Vrijsen, Geert; Flammia, Steven T.; Brown, Kenneth R.; Maunz, Peter; Kim, Jungsang

    2015-12-01

    The fidelity of laser-driven quantum logic operations on trapped ion qubits tend to be lower than microwave-driven logic operations due to the difficulty of stabilizing the driving fields at the ion location. Through stabilization of the driving optical fields and use of composite pulse sequences, we demonstrate high-fidelity single-qubit gates for the hyperfine qubit of a 171/SUPYb+ ion trapped in a microfabricated surface-electrode ion trap. Gate error is characterized using a randomized benchmarking protocol and an average error per randomized Clifford group gate of 3.6 (3 ) ×10-4 is measured. We also report experimental realization of palindromic pulse sequences that scale efficiently in sequence length.

  2. Molecular self-assembly at bare semiconductor surfaces: preparation and characterization of highly organized octadecanethiolate monolayers on GaAs(001).

    PubMed

    McGuiness, Christine L; Shaporenko, Andrey; Mars, Carole K; Uppili, Sundararajan; Zharnikov, Michael; Allara, David L

    2006-04-19

    Through rigorous control of preparation conditions, organized monolayers with a highly reproducible structure can be formed by solution self-assembly of octadecanethiol on GaAs (001) at ambient temperature. A combination of characterization probes reveal a structure with conformationally ordered alkyl chains tilted on average at 14 +/- 1 degrees from the surface normal with a 43 +/- 5 degrees twist, a highly oleophobic and hydrophobic ambient surface, and direct S-GaAs attachment. Analysis of the tilt angle and film thickness data shows a significant mismatch of the average adsorbate molecule spacings with the spacings of an intrinsic GaAs(001) surface lattice. The monolayers are stable up to approximately 100 degrees C and exhibit an overall thermal stability which is lower than that of the same monolayers on Au[111] surfaces. A two-step solution assembly process is observed: rapid adsorption of molecules over the first several hours to form disordered structures with molecules lying close to the substrate surface, followed by a slow densification and asymptotic approach to final ordering. This process, while similar to the assembly of alkanethiols on Au[111], is nearly 2 orders of magnitude slower. Finally, despite differences in assembly rates and the thermal stability, exchange experiments with isotopically tagged molecules show that the octadecanethiol on GaAs(001) monolayers undergo exchange with solute thiol molecules at roughly the same rate as the corresponding exchanges of the same monolayers on Au[111]. PMID:16608359

  3. Molecular-level insights of early-stage prion protein aggregation on mica and gold surface determined by AFM imaging and molecular simulation.

    PubMed

    Lou, Zhichao; Wang, Bin; Guo, Cunlan; Wang, Kun; Zhang, Haiqian; Xu, Bingqian

    2015-11-01

    By in situ time-lapse AFM, we investigated early-stage aggregates of PrP formed at low concentration (100 ng/mL) on mica and Au(111) surfaces in acetate buffer (pH 4.5). Remarkably different PrP assemblies were observed. Oligomeric structures of PrP aggregates were observed on mica surface, which was in sharp contrast to the multi-layer PrP aggregates yielding parallel linear patterns observed Au(111) surface. Combining molecular dynamics and docking simulations, PrP monomers, dimers and trimers were revealed as the basic units of the observed aggregates. Besides, the mechanisms of the observed PrP aggregations and the corresponding molecular-substrate and intermolecular interactions were suggested. These interactions involved gold-sulfur interaction, electrostatic interaction, hydrophobic interaction, and hydrogen binding interaction. In contrast, the PrP aggregates observed in pH 7.2 PBS buffer demonstrated similar large ball-like structures on both mica and Au(111) surfaces. The results indicate that the pH of a solution and the surface of the system can have strong effects on supramolecular assemblies of prion proteins. This study provides in-depth understanding on the structural and mechanistic nature of PrP aggregation, and can be used to study the aggregation mechanisms of other proteins with similar misfolding properties.

  4. Molecular self-assembly at bare semiconductor surfaces: preparation and characterization of highly organized octadecanethiolate monolayers on GaAs(001).

    PubMed

    McGuiness, Christine L; Shaporenko, Andrey; Mars, Carole K; Uppili, Sundararajan; Zharnikov, Michael; Allara, David L

    2006-04-19

    Through rigorous control of preparation conditions, organized monolayers with a highly reproducible structure can be formed by solution self-assembly of octadecanethiol on GaAs (001) at ambient temperature. A combination of characterization probes reveal a structure with conformationally ordered alkyl chains tilted on average at 14 +/- 1 degrees from the surface normal with a 43 +/- 5 degrees twist, a highly oleophobic and hydrophobic ambient surface, and direct S-GaAs attachment. Analysis of the tilt angle and film thickness data shows a significant mismatch of the average adsorbate molecule spacings with the spacings of an intrinsic GaAs(001) surface lattice. The monolayers are stable up to approximately 100 degrees C and exhibit an overall thermal stability which is lower than that of the same monolayers on Au[111] surfaces. A two-step solution assembly process is observed: rapid adsorption of molecules over the first several hours to form disordered structures with molecules lying close to the substrate surface, followed by a slow densification and asymptotic approach to final ordering. This process, while similar to the assembly of alkanethiols on Au[111], is nearly 2 orders of magnitude slower. Finally, despite differences in assembly rates and the thermal stability, exchange experiments with isotopically tagged molecules show that the octadecanethiol on GaAs(001) monolayers undergo exchange with solute thiol molecules at roughly the same rate as the corresponding exchanges of the same monolayers on Au[111].

  5. Study of SAM surface morphology, integrity and film quality on various Au surfaces

    NASA Astrophysics Data System (ADS)

    Murphy, John; Senevirathne, Indrajith

    2013-03-01

    SAM (Self Assembled Monolayer) surfaces have many possible applications from polymer based electronics to sensor engineering. Common substrate architecture for such systems happens to be Au(111) on mica. Au on layered mica lacks mechanical resilience towards engineering applications. Solutions of 1-dodecanethiol (hydrophobic -R), dissolved in 200 proof Ethanol with 5mM concentration were prepared. These solutions were used in developing SAMs on purchased, clean flat Au(111) on mica (standard), Au sputter deposited on mica, Hydrogen flame annealed Au layers on glass, and Hydrogen flame annealed Au layers on mica. Resulting SAM surfaces were investigated with regular and custom built hydrophilic and hydrophobic AFM (Atomic Force Microcopy) probes via contact, and non contact AFM with topography and phase imaging. Surface integrity, roughness, corrugation and morphology on SAM surfaces were estimated. Preliminary data indicated total RMS surface roughness at ~ 2.8nm for SAMs on typical gold surfaces on mica purchased (standard) while varying RMS surface roughness estimates on subsequent surfaces with flame annealed samples showing similar RMS surface roughness. LHU Nanotechnology Program, PASSHE FPDC (LOU # 2010-LHU-03).

  6. Electrochemical oxidation of ampicillin antibiotic at boron-doped diamond electrodes and process optimization using response surface methodology.

    PubMed

    Körbahti, Bahadır K; Taşyürek, Selin

    2015-03-01

    Electrochemical oxidation and process optimization of ampicillin antibiotic at boron-doped diamond electrodes (BDD) were investigated in a batch electrochemical reactor. The influence of operating parameters, such as ampicillin concentration, electrolyte concentration, current density, and reaction temperature, on ampicillin removal, COD removal, and energy consumption was analyzed in order to optimize the electrochemical oxidation process under specified cost-driven constraints using response surface methodology. Quadratic models for the responses satisfied the assumptions of the analysis of variance well according to normal probability, studentized residuals, and outlier t residual plots. Residual plots followed a normal distribution, and outlier t values indicated that the approximations of the fitted models to the quadratic response surfaces were very good. Optimum operating conditions were determined at 618 mg/L ampicillin concentration, 3.6 g/L electrolyte concentration, 13.4 mA/cm(2) current density, and 36 °C reaction temperature. Under response surface optimized conditions, ampicillin removal, COD removal, and energy consumption were obtained as 97.1 %, 92.5 %, and 71.7 kWh/kg CODr, respectively.

  7. Electrochemical oxidation of ampicillin antibiotic at boron-doped diamond electrodes and process optimization using response surface methodology.

    PubMed

    Körbahti, Bahadır K; Taşyürek, Selin

    2015-03-01

    Electrochemical oxidation and process optimization of ampicillin antibiotic at boron-doped diamond electrodes (BDD) were investigated in a batch electrochemical reactor. The influence of operating parameters, such as ampicillin concentration, electrolyte concentration, current density, and reaction temperature, on ampicillin removal, COD removal, and energy consumption was analyzed in order to optimize the electrochemical oxidation process under specified cost-driven constraints using response surface methodology. Quadratic models for the responses satisfied the assumptions of the analysis of variance well according to normal probability, studentized residuals, and outlier t residual plots. Residual plots followed a normal distribution, and outlier t values indicated that the approximations of the fitted models to the quadratic response surfaces were very good. Optimum operating conditions were determined at 618 mg/L ampicillin concentration, 3.6 g/L electrolyte concentration, 13.4 mA/cm(2) current density, and 36 °C reaction temperature. Under response surface optimized conditions, ampicillin removal, COD removal, and energy consumption were obtained as 97.1 %, 92.5 %, and 71.7 kWh/kg CODr, respectively. PMID:24906830

  8. From HCOOH to CO at Pd electrodes: a surface-enhanced infrared spectroscopy study.

    PubMed

    Wang, Jin-Yi; Zhang, Han-Xuan; Jiang, Kun; Cai, Wen-Bin

    2011-09-28

    The decomposition of HCOOH on Pd surfaces over a potential range of practical relevance to hydrogen production and fuel cell anode operation was probed by combining high-sensitivity in situ surface-enhanced IR spectroscopy with attenuated total reflection and thin-layer flow cell configurations. For the first time, concrete spectral evidence of CO(ad) formation has been obtained, and a new main pathway from HCOOH to CO(ad) involving the reduction of the dehydrogenation product of HCOOH (i.e., CO(2)) is proposed. PMID:21882830

  9. Intervalence transfer of ferrocene moieties adsorbed on electrode surfaces by a conjugated linkage

    NASA Astrophysics Data System (ADS)

    Chen, Wei; Brown, Lauren E.; Konopelski, Joseph P.; Chen, Shaowei

    2009-03-01

    Effective intervalence transfer occurred between the metal centers of ferrocene moieties that were adsorbed onto a ruthenium thin film surface by ruthenium-carbene π bonds, a direct verification of Hush's four-decade-old prediction. Electrochemical measurements showed two pairs of voltammetric peaks where the separation of the formal potentials suggested a Class II behavior. Additionally, the potential spacing increased with increasing ferrocene surface coverage, most probably as a consequence of the enhanced contribution from through-space electronic interactions between the metal centers. In contrast, the incorporation of a sp 3 carbon spacer into the ferrocene-ruthenium linkage led to the diminishment of interfacial electronic communication.

  10. Enhancing Electrochemical Water-Splitting Kinetics by Polarization-Driven Formation of Near-Surface Iron(0): An In Situ XPS Study on Perovskite-Type Electrodes**

    PubMed Central

    Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Rameshan, Raffael; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Fleig, Jürgen; Klötzer, Bernhard

    2015-01-01

    In the search for optimized cathode materials for high-temperature electrolysis, mixed conducting oxides are highly promising candidates. This study deals with fundamentally novel insights into the relation between surface chemistry and electrocatalytic activity of lanthanum ferrite based electrolysis cathodes. For this means, near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and impedance spectroscopy experiments were performed simultaneously on electrochemically polarized La0.6Sr0.4FeO3−δ (LSF) thin film electrodes. Under cathodic polarization the formation of Fe0 on the LSF surface could be observed, which was accompanied by a strong improvement of the electrochemical water splitting activity of the electrodes. This correlation suggests a fundamentally different water splitting mechanism in presence of the metallic iron species and may open novel paths in the search for electrodes with increased water splitting activity. PMID:25557533

  11. Wiring of the aldehyde oxidoreductase PaoABC to electrode surfaces via entrapment in low potential phenothiazine-modified redox polymers.

    PubMed

    Pinyou, Piyanut; Ruff, Adrian; Pöller, Sascha; Alsaoub, Sabine; Leimkühler, Silke; Wollenberger, Ulla; Schuhmann, Wolfgang

    2016-06-01

    Phenothiazine-modified redox hydrogels were synthesized and used for the wiring of the aldehyde oxidoreductase PaoABC to electrode surfaces. The effects of the pH value and electrode surface modification on the biocatalytic activity of the layers were studied in the presence of vanillin as the substrate. The enzyme electrodes were successfully employed as bioanodes in vanillin/O2 biofuel cells in combination with a high potential bilirubin oxidase biocathode. Open circuit voltages of around 700 mV could be obtained in a two compartment biofuel cell setup. Moreover, the use of a rather hydrophobic polymer with a high degree of crosslinking sites ensures the formation of stable polymer/enzyme films which were successfully used as bioanode in membrane-less biofuel cells. PMID:26775204

  12. Enhancing electrochemical water-splitting kinetics by polarization-driven formation of near-surface iron(0): an in situ XPS study on perovskite-type electrodes.

    PubMed

    Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Rameshan, Raffael; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Fleig, Jürgen; Klötzer, Bernhard

    2015-02-23

    In the search for optimized cathode materials for high-temperature electrolysis, mixed conducting oxides are highly promising candidates. This study deals with fundamentally novel insights into the relation between surface chemistry and electrocatalytic activity of lanthanum ferrite based electrolysis cathodes. For this means, near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and impedance spectroscopy experiments were performed simultaneously on electrochemically polarized La0.6 Sr0.4 FeO3-δ (LSF) thin film electrodes. Under cathodic polarization the formation of Fe(0) on the LSF surface could be observed, which was accompanied by a strong improvement of the electrochemical water splitting activity of the electrodes. This correlation suggests a fundamentally different water splitting mechanism in presence of the metallic iron species and may open novel paths in the search for electrodes with increased water splitting activity.

  13. Assembly of selective biomimetic surface on an electrode surface: a design of nano-bio interface for biosensing.

    PubMed

    Gao, Tao; Liu, Fengzhen; Yang, Dawei; Yu, Yue; Wang, Zhaoxia; Li, Genxi

    2015-06-01

    In nature, cellular molecule sensing is usually achieved at the environment/membrane interface. In the meantime, rapid growth of nanotechnology is increasingly pushing engineered nanomaterials to interact with biological surfaces. Herein, inspired by trans-membrane signal transduction, a nano-bio interface has been constructed in this work for biosensing application. The interface is formed between a selective biomembrane mimetic surface (SBMMS) and a function-oriented 2D nanohybrid. Based on the design, target recognition can be performed in a biologically favorable environment, and the nano-bio interaction can be transduced into amplified electrochemical readouts. Furthermore, this sensing platform can be used to analyze various kinds of targets, including proteins, nucleic acids, and small molecules, just by changing the biorecognition element. Low detection limits and wide detection ranges can also be obtained. So, this nano-bio interface may provide a new platform for bioanalytical research in the future.

  14. Structure and surface chemistry of Al2O3 coated LiMn2O4 nanostructured electrodes with improved lifetime

    NASA Astrophysics Data System (ADS)

    Waller, G. H.; Brooke, P. D.; Rainwater, B. H.; Lai, S. Y.; Hu, R.; Ding, Y.; Alamgir, F. M.; Sandhage, K. H.; Liu, M. L.

    2016-02-01

    Aluminum oxide coatings deposited on LiMn2O4/carbon fiber electrodes by atomic layer deposition (ALD) are shown to enhance cathode performance in lithium-ion batteries. With a thin Al2O3 coating derived from 10 ALD cycles, the electrodes exhibit 2.5 times greater capacity retention over 500 cycles at a rate of 1C as well as enhanced rate capability and decreased polarization resistance. Structural and surface studies of the electrodes before and after cycling reveal that a near-surface phenomenon is responsible for the improved electrochemical performance. The crystal structure and overall morphology of the LiMn2O4 electrode are found to be unaffected by electrochemical cycling, both for coated and uncoated samples. However, evidence of Mn diffusion into the ALD coatings is observed from both transmission electron microscopy/energy-dispersive X-ray spectroscopy (TEM-EDS) and X-ray Photoelectron Spectroscopy (XPS) after electrochemical cycling. Furthermore, XPS analysis of the Al 2p photoemission peak for the ALD coated electrodes reveal a significant shift in binding energy and peak shape, suggesting the presence of an Al-O-F compound formed by sequestering HF in the electrolyte. These observations provide new insight toward understanding the mechanism in which ultrathin coatings of amphoteric oxides can inhibit capacity loss for LiMn2O4 cathodes in lithium-ion batteries.

  15. Experimental Approach to Controllably Vary Protein Oxidation While Minimizing Electrode Adsorption for Boron-Doped Diamond Electrochemical Surface Mapping Applications

    SciTech Connect

    McClintock, Carlee; Hettich, Robert {Bob} L

    2013-01-01

    Oxidative protein surface mapping has become a powerful approach for measuring the solvent accessibility of folded protein structures. A variety of techniques exist for generating the key reagent hydroxyl radicals for these measurements; however, many of these approaches require use of radioactive sources or caustic oxidizing chemicals. The purpose of this research was to evaluate and optimize the use of boron-doped diamond (BDD) electrochemistry as a highly accessible tool for producing hydroxyl radicals as a means to induce a controllable level of oxidation on a range of intact proteins. These experiments utilize a relatively high flow rates to reduce protein residence time inside the electrochemical flow chamber, along with a unique cell activation approach to improve control over the intact protein oxidation yield. Studies were conducted to evaluate the level of protein adsorption onto the electrode surface. This report demonstrates a robust protocol for the use of BDD electrochemistry and high performance LC-MS/MS as a high-throughput experimental pipeline for probing higher order protein structure, and illustrates how it is complementary to predictive computational modeling efforts.

  16. Note: electrode polarization of Galinstan electrodes for liquid impedance spectroscopy.

    PubMed

    Mellor, Brett L; Kellis, Nathan A; Mazzeo, Brian A

    2011-04-01

    Electrode polarization is a significant obstacle in the impedance measurements of ionic liquids. An atomically smooth electrode surface could potentially reduce unwanted impedance contributions from electrode polarization. Liquid metal electrodes were formed by adhering Galinstan to acrylic plates in a parallel-plate capacitor arrangement. Electrode polarization was compared to a similar cell with stainless steel electrodes. The impedance of salt and protein solutions (β-lactoglobulin) was measured from 40 Hz to 110 MHz. Because of oxide layer formation, the performance of the Galinstan electrode is significantly different than the theoretical ideal.

  17. Note: Electrode polarization of Galinstan electrodes for liquid impedance spectroscopy

    NASA Astrophysics Data System (ADS)

    Mellor, Brett L.; Kellis, Nathan A.; Mazzeo, Brian A.

    2011-04-01

    Electrode polarization is a significant obstacle in the impedance measurements of ionic liquids. An atomically smooth electrode surface could potentially reduce unwanted impedance contributions from electrode polarization. Liquid metal electrodes were formed by adhering Galinstan to acrylic plates in a parallel-plate capacitor arrangement. Electrode polarization was compared to a similar cell with stainless steel electrodes. The impedance of salt and protein solutions (β-lactoglobulin) was measured from 40 Hz to 110 MHz. Because of oxide layer formation, the performance of the Galinstan electrode is significantly different than the theoretical ideal.

  18. Electrospun lignin-derived carbon nanofiber mats surface-decorated with MnO2 nanowhiskers as binder-free supercapacitor electrodes with high performance

    NASA Astrophysics Data System (ADS)

    Ma, Xiaojing; Kolla, Praveen; Zhao, Yong; Smirnova, Alevtina L.; Fong, Hao

    2016-09-01

    The aim of this study is to explore innovative materials for the development of next-generation supercapacitor electrodes. The hypothesis is that, upon the surface-decoration with appropriate amount of MnO2 nanowhiskers, freestanding and highly graphitic electrospun carbon nanofiber (ECNF) mats (with fiber diameters of ∼200 nm and BET specific surface areas of ∼583 m2 g-1) derived from a natural product of lignin would be binder-free supercapacitor electrodes with high performance. To test the hypothesis, the ECNF mats have been prepared first; thereafter, the acquired ECNF mats have been surface-decorated with varied amounts of MnO2 nanowhiskers to prepare three types of ECNF/MnO2 mats. The morphological and structural properties of ECNF and ECNF/MnO2 mats are characterized by SEM, TEM and XRD, the weight percentages of MnO2 nanowhiskers in three ECNF/MnO2 mats are determined by thermal gravimetric analysis; while the electrochemical performance of each mat/electrode is evaluated by cyclic voltammetry, galvanostatic charge/discharge method, and electrochemical impedance spectroscopy. This study reveals that, all of the three ECNF/MnO2 mats/electrodes have significantly enhanced electrochemical performances compared to the ECNF mat/electrode; while the ECNF/MnO2 (1:1) mat/electrode exhibits the highest gravimetric capacitance of 83.3 F g-1, energy density of 84.3 W h kg-1, and power density of 5.72 kW kg-1.

  19. Synthesis and characterization of high surface area molybdenum nitride electrodes for high energy density electrochemical storage devices

    NASA Astrophysics Data System (ADS)

    Roberson, Scott Lee

    1998-12-01

    Polycrystalline high surface area (>20 msp2/g) Mosb{x}N (x = 1 and 2) films have been synthesized by the conversion of MoOsb3 films in controlled temperature reactions with NHsb3 and by chemical vapor deposition (CVD) of either MoClsb5 or Mo(CO)sb6 and NHsb3. The formation of larger surface areas was achieved in films that were converted form MoOsb3; however, control of the composition of the Mosb{x}N films was achieved only by CVD. The increase in surface areas in the converted samples was credited to both the increase in specific density of the film during the conversion to Mosb{x}N and the topotactic nature of the conversion. Compositional control of the CVD Mosb{x}N films was accomplished by varying the deposition rate, the precursor employed, the deposition temperature and the NHsb3 flow rate. The electrochemical stability of the converted and CVD Mosb{x}N films occurred between ≈0.5 and ≈0.70 V vs. a standard hydrogen electrode (SHE). Control of the composition of the CVD Mosb{x}N films allowed the determination of the electrochemical stabilities of each phase (gamma-Mosb2N and delta-MoN). The CVD Mosb{x}N films were subsequently used as cathodes for the fabrication of hybrid capacitor devices. These devices were operational between 0-50 V and had a total capacitance of 5.0 mF at 1 V. Both the operating voltage and the capacitance of these devices are higher than devices currently used in government and medical applications.

  20. Smooth electrode and method of fabricating same

    DOEpatents

    Weaver, Stanton Earl; Kennerly, Stacey Joy; Aimi, Marco Francesco

    2012-08-14

    A smooth electrode is provided. The smooth electrode includes at least one metal layer having thickness greater than about 1 micron; wherein an average surface roughness of the smooth electrode is less than about 10 nm.

  1. Nanoscopic electrode molecular probes

    DOEpatents

    Krstic, Predrag S.; Meunier, Vincent

    2012-05-22

    The present invention relates to a method and apparatus for enhancing the electron transport property measurements of a molecule when the molecule is placed between chemically functionalized carbon-based nanoscopic electrodes to which a suitable voltage bias is applied. The invention includes selecting a dopant atom for the nanoscopic electrodes, the dopant atoms being chemically similar to atoms present in the molecule, and functionalizing the outer surface and terminations of the electrodes with the dopant atoms.

  2. Concentration and density changes at an electrode surface and the principle of unchanging total concentration

    DOE PAGES

    Stephen W. Feldberg; Lewis, Ernie R.

    2016-02-17

    In this study, the principle of unchanging total concentration as described by Oldham and Feldberg [J. Phys. Chem. B, 103, 1699 (1999)] is invoked to analyze systems comprising a redox pair (Xz11 and Xz22) plus one or more non-electroactive species (Xz33,Xz44...Xzjmaxjmax) where Xzjj is the jth species with charge zj and concentration; cj. The principle states that if the diffusion coefficients for all species are identical and mass transport is governed by the Nernst-Planck expression, the total concentration does not change during any electrochemical perturbation, i.e.: Σjmaxj=1[Xzjj]=Σjmaxj=1 cj = SP With this principle we deduce the electrochemically induced difference betweenmore » the surface and bulk concentrations for each species. Those concentration differences are translated into density differences which are a function of the density of the solvent and of the concentration differences, molecular masses and the standard partial molar volumes of all species. Those density differences in turn can induce convection that will ultimately modify the observed current. However, we did not attempt to quantify details of the natural convection and current modification produced by those density differences.« less

  3. Pd-Au nanoparticle decorated carbon nanotube as a sensing layer on the surface of glassy carbon electrode for electrochemical determination of ceftazidime.

    PubMed

    Shahrokhian, Saeed; Salimian, Razieh; Rastgar, Shokoufeh

    2014-01-01

    A simple electrodeposition method is employed to construct a thin film modifier of palladium-gold nanoparticles (Pd-AuNPs) decorated multi-walled carbon nanotube (MWCNT) on the surface of glassy carbon electrode (GCE). Morphology and property of Pd-AuNPs-MWCNT have been examined by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Electrochemical performance of Pd-AuNPs-MWCNT/GCE for detection of ceftazidime (CFZ) has been investigated by cyclic voltammetry (CV). This nanostructured film modified electrode effectively exhibited enhanced properties for detection of ceftazidime (CFZ). The effects of various experimental variables such as, the amount of casted MWCNT, time and potential of deposition of metal nanoparticles and the pH of the buffered solution on the electrode response are optimized. The proposed electrode showed a linear dynamic range of 0.05-50μM and the detection limit of 1nM for the CFZ. The modified electrode successfully supports the sensitive detection of trace amounts of the CFZ in pharmaceutical and clinical preparations.

  4. Electrocatalytic determination of sumatriptan on the surface of carbon-paste electrode modified with a composite of cobalt/Schiff-base complex and carbon nanotube.

    PubMed

    Amiri, Mandana; Pakdel, Zohreh; Bezaatpour, Abolfazl; Shahrokhian, Saeed

    2011-06-01

    The electrochemical oxidation of sumatriptan on the surface of carbon paste electrode modified with multi-walled carbon nanotube and cobalt methyl-salophen complex is studied by using cyclic voltammetry and polarization studies. The results indicate that the drug is irreversibly oxidized in a one electron oxidation mechanism. It was found that the peak potential shifted negatively with increasing pH, confirms that H(+) participate in the oxidation process. The electrode is shown to be very effective for the detection of sumatriptan in the presence of other biological reductant compounds. The prepared modified electrode exhibits a very good resolution between the voltammetric peaks of sumatriptan, ascorbic acid and uric acid, which makes it suitable for the simultaneous detection of sumatriptan in the presence of these compounds in clinical and pharmaceutical preparations. It can be concluded that multi-walled carbon nanotube and Shiff base complex have synergic effect on electroacatalytic oxidation of sumatriptan. A linear range of 1-1000μM and detection limit of 0.3μM was obtained for sumatriptan from DPV measurements using this electrode in 0.1M acetate buffered solution of pH 5.0. The electrode has been applied successfully for the determination of sumatriptan in synthetic serum and commercial tablets.

  5. Reversibly immobilized biological materials in monolayer films on electrodes

    SciTech Connect

    Weaver, P.F.; Frank, A.J.

    1991-04-08

    A method is provided for reversibly binding charged biological particles in a fluid medium to an electrode surface. The method comprises treating (e.g., derivatizing) the electrode surface with an electrochemically active material; connecting the electrode to an electrical potential; and exposing the fluid medium to the electrode surface in a manner such that the charged particles become adsorbed on the electrode surface.

  6. The Influence of Electrode Surface Mercury Film Deformation on the Breakdown Voltage of a Sub-Nanosecond Pulse Discharge Tube

    NASA Astrophysics Data System (ADS)

    Weng, Ming; Xu, Weijun; Wang, Rui

    2012-11-01

    A sub-nanosecond pulse discharge tube is a gas discharge tube which can generate a rapid high-voltage pulse of kilo-volts in amplitude and sub-nanoseconds in width. In this paper, the sub-nanosecond pulse discharge tube and its working principles are described. Because of the phenomenon that the deformation process of the mercury film on the electrode surface lags behind the charging process, the mercury film deformation process affects the dynamic breakdown voltage of the tube directly. The deformation of the mercury film is observed microscopically, and the dynamic breakdown voltage of the tube is measured using an oscillograph. The results show that all the parameters in the charging process, such as charging resistance, charging capacitance and DC power supply, affect the dynamic breakdown voltage of the tube. Based on these studies, the output pulse amplitude can be controlled continuously and individually by adjusting the power supply voltage. When the DC power supply is adjusted from 7 kV to 10 kV, the dynamic breakdown voltage ranges from 6.5 kV to 10 kV. According to our research, a kind of sub-nanosecond pulse generator is made, with a pulse width ranging from 0.5 ns to 2.5 ns, a rise time from 0.32 ns to 0.58 ns, and a pulse amplitude that is adjustable from 1.5 kV to 5 kV.

  7. Surface analysis and electrochemistry of a robust carbon-nanofiber-based electrode platform H2O2 sensor

    NASA Astrophysics Data System (ADS)

    Suazo-Dávila, D.; Rivera-Meléndez, J.; Koehne, J.; Meyyappan, M.; Cabrera, C. R.

    2016-10-01

    A vertically aligned carbon nanofiber-based (VACNF) electrode platform was developed for an enzymeless hydrogen peroxide sensor. Vertical nanofibers have heights on the order of 2-3 μm, and diameters that vary from 50 to 100 nm as seen by atomic force microscopy. The VACNF was grown as individual, vertically, and freestanding structures using plasma-enhanced chemical vapor deposition. The electrochemical sensor, for the hydrogen peroxide measurement in solution, showed stability and reproducibility in five consecutive calibration curves with different hydrogen peroxide concentrations over a period of 3 days. The detection limit was 66 μM. The sensitivity for hydrogen peroxide electrochemical detection was 0.0906 mA cm-2 mM-1, respectively. The sensor was also used for the measurement of hydrogen peroxide as the by-product of the reaction of cholesterol with cholesterol oxidase as a biosensor application. The sensor exhibits linear behavior in the range of 50 μM-1 mM in cholesterol concentrations. The surface analysis and electrochemistry characterization is presented.

  8. Surface potential distribution and airflow performance of different air-exposed electrode plasma actuators at different alternating current/direct current voltages

    SciTech Connect

    Yang, Liang; Yan, Hui-Jie; Qi, Xiao-Hua; Hua, Yue; Ren, Chun-Sheng

    2015-04-15

    Asymmetric surface dielectric barrier discharge (SDBD) plasma actuators have been intensely studied for a number of years due to their potential applications for aerodynamic control. In this paper, four types of actuators with different configurations of exposed electrode are proposed. The SDBD actuators investigated are driven by dual-power supply, referred to as a fixed AC high voltage and an adjustable DC bias. The effects of the electrode structures on the dielectric surface potential distribution, the electric wind velocity, and the mean thrust production are studied, and the dominative factors of airflow acceleration behavior are revealed. The results have shown that the actions of the SDBD actuator are mainly dependent on the geometry of the exposed electrode. Besides, the surface potential distribution can effectively affect the airflow acceleration behavior. With the application of an appropriate additional DC bias, the surface potential will be modified. As a result, the performance of the electric wind produced by a single SDBD can be significantly improved. In addition, the work also illustrates that the actuators with more negative surface potential present better mechanical performance.

  9. Surface properties and graphitization of polyacrylonitrile based fiber electrodes affecting the negative half-cell reaction in vanadium redox flow batteries

    NASA Astrophysics Data System (ADS)

    Langner, J.; Bruns, M.; Dixon, D.; Nefedov, A.; Wöll, Ch.; Scheiba, F.; Ehrenberg, H.; Roth, C.; Melke, J.

    2016-07-01

    Carbon felt electrodes for vanadium redox flow batteries are obtained by the graphitization of polyacrylonitrile based felts at different temperatures. Subsequently, the surface of the felts is modified via thermal oxidation at various temperatures. A single-cell experiment shows that the voltage efficiency is increased by this treatment. Electrode potentials measured with reference electrode setup show that this voltage efficiency increase is caused mainly by a reduction of the overpotential of the negative half-cell reaction. Consequently, this reaction is investigated further by cyclic voltammetry and the electrode activity is correlated with structural and surface chemical properties of the carbon fibers. By Raman, X-ray photoelectron and near edge X-ray absorption fine structure spectroscopy the role of edge sites and oxygen containing functional groups (OCFs) for the electrochemical activity are elucidated. A significant activity increase is observed in correlation with these two characteristics. The amount of OCFs is correlated with structural defects (e.g. edge sites) of the carbon fibers and therefore decreases with an increasing graphitization degree. Thus, for the same thermal oxidation temperature carbon fibers graphitized at a lower temperature show higher activities than those graphitized at a higher temperature.

  10. Characterization of p-type CdTe electrodes in acetonitrile/electrolyte solutions. Nearly ideal behavior from reductive surface pretreatments

    NASA Astrophysics Data System (ADS)

    White, H. S.; Ricco, A. J.; Wrighton, M. S.

    1983-06-01

    Single crystal p-CdTe (Eg equal 1.4 eV) electrodes have been characterized in CH3CN/electrolyte solutions. Deliberate modification of the p-CdTe surface by etching in strongly oxidizing (Cr2072-/HNO3) or reducing (S2042-/OH-) solutions alters the p-CdTe surface to give rise to large differences in the electrochemical response in the dark and under illumination. The oxidative pretreatment apparently yields a p-CdTe surface that is Fermi level pinned, whereas the reductive pretreatment yields nearly ideal response. The pretreated electrodes were characterized by XPS, impedance measurements, and cyclic voltammetry in the presence of a number of reversible, one-electron redox couples. XPS indicates the presence of a number of reversible, one-electron redox couples. XPS indicates the presence of a Te-rich surface overlayer, composed of Te0 and Te02, on CdTe etched in oxidizing media. Electrodes etched in reducing solutions yield XPS spectra nearly identical to those of an Ar ion-sputtered CdTe sample, in terms of stoichiometry (1:1) and chemical state (Cd2+ and Te2-) of cadmium and telluride.

  11. Secondary-electron-emission losses in multistage depressed collectors and traveling-wave-tube efficiency improvements with carbon collector electrode surfaces

    NASA Technical Reports Server (NTRS)

    Ramins, P.; Ebihara, B. T.

    1986-01-01

    Secondary-electron-emission losses in multistage depressed collectors (MDC's) and their effects on overall traveling-wave-tube (TWT) efficiency were investigated. Two representative TWT's and several computer-modeled MDC's were used. The experimental techniques provide the measurement of both the TWT overall and the collector efficiencies. The TWT-MDC performance was optimized and measured over a wide range of operating conditions, with geometrically identical collectors, which utilized different electrode surface materials. Comparisons of the performance of copper electrodes to that of various forms of carbon, including pyrolytic and iisotropic graphites, were stressed. The results indicate that: (1) a significant improvement in the TWT overall efficiency was obtained in all cases by the use of carbon, rather than copper electrodes, and (2) that the extent of this efficiency enhancement depended on the characteristics of the TWT, the TWT operating point, the MDC design, and collector voltages. Ion textured graphite was found to be particularly effective in minimizing the secondary-electron-emission losses. Experimental and analytical results, however, indicate that it is at least as important to provide a maximum amount of electrostatic suppression of secondary electrons by proper MDC design. Such suppression, which is obtained by ensuring that a substantial suppressing electric field exists over the regions of the electrodes where most of the current is incident, was found to be very effective. Experimental results indicate that, with proper MDC design and the use of electrode surfaces with low secondary-electron yield, degradation of the collector efficiency can be limited to a few percent.

  12. [Atomic beam studies of the interaction of hydrogen with transition metal surfaces

    SciTech Connect

    Not Available

    1992-01-01

    We have constructed two experimental facilities during the term of this grant. In the first three years we constructed a helium atom scattering (HAS) facility with both elastic (EHAS) and inelastic (IHAS) scattering measurement capabilities to investigate the structural and dynamical aspects of solid surfaces and thin films. A pioneering surface metastable atom magnetic diffraction (SMAMD) facility was constructed and developed over the past four years, which makes possible the investigation of long-range electron spin-ordering on the surfaces of insulating magnetic crystals. The following were studied: H overlayers and Ag, Cu on Pd(111), reconstructed Au(111), and NiO(100).

  13. Immobilization of the [FeFe]-hydrogenase CrHydA1 on a gold electrode: design of a catalytic surface for the production of molecular hydrogen.

    PubMed

    Krassen, Henning; Stripp, Sven; von Abendroth, Gregory; Ataka, Kenichi; Happe, Thomas; Heberle, Joachim

    2009-06-01

    Hydrogenase-modified electrodes are a promising catalytic surface for the electrolysis of water with an overpotential close to zero. The [FeFe]-hydrogenase CrHydA1 from the photosynthetic green alga Chlamydomonas reinhardtii is the smallest [FeFe]-hydrogenase known and exhibits an extraordinary high hydrogen evolution activity. For the first time, we immobilized CrHydA1 on a gold surface which was modified by different carboxy-terminated self-assembled monolayers. The immobilization was in situ monitored by surface-enhanced infrared spectroscopy. In the presence of the electron mediator methyl viologen the electron transfer from the electrode to the hydrogenase was detected by cyclic voltammetry. The hydrogen evolution potential (-290 mV vs NHE, pH 6.8) of this protein modified electrode is close to the value for bare platinum (-270 mV vs NHE). The surface coverage by CrHydA1 was determined to 2.25 ng mm(-2) by surface plasmon resonance, which is consistent with the formation of a protein monolayer. Hydrogen evolution was quantified by gas chromatography and the specific hydrogen evolution activity of surface-bound CrHydA1 was calculated to 1.3 micromol H(2)min(-1)mg(-1) (or 85 mol H(2)min(-1)mol(-1)). In conclusion, a viable hydrogen-evolving surface was developed that may be employed in combination with immobilized photosystems to provide a platform for hydrogen production from water and solar energy with enzymes as catalysts. PMID:19480942

  14. An Experimental Approach to Controllably Vary Protein Oxidation While Minimizing Electrode Adsorption for Boron-Doped Diamond Electrochemical Surface Mapping Applications

    PubMed Central

    McClintock, Carlee S; Hettich, Robert L.

    2012-01-01

    Oxidative protein surface mapping has become a powerful approach for measuring the solvent accessibility of folded protein structures. A variety of techniques exist for generating the key reagent – hydroxyl radicals – for these measurements; however, these approaches range significantly in their complexity and expense of operation. This research expands upon earlier work to enhance the controllability of boron-doped diamond (BDD) electrochemistry as an easily accessible tool for producing hydroxyl radicals in order to oxidize a range of intact proteins. Efforts to modulate oxidation level while minimizing the adsorption of protein to the electrode involved the use of relatively high flow rates to reduce protein residence time inside the electrochemical flow chamber. Additionally, a different cell activation approach using variable voltage to supply a controlled current allowed us to precisely tune the extent of oxidation in a protein-dependent manner. In order to gain perspective on the level of protein adsorption onto the electrode surface, studies were conducted to monitor protein concentration during electrolysis and gauge changes in the electrode surface between cell activation events. This report demonstrates the successful use of BDD electrochemistry for greater precision in generating a target number of oxidation events upon intact proteins. PMID:23210708

  15. Influence of surface adsorption on the interfacial electron transfer of flavin adenine dinucleotide and glucose oxidase at carbon nanotube and nitrogen-doped carbon nanotube electrodes.

    PubMed

    Goran, Jacob M; Mantilla, Sandra M; Stevenson, Keith J

    2013-02-01

    The adsorption of flavin adenine dinucleotide (FAD) and glucose oxidase (GOx) onto carbon nanotube (CNT) and nitrogen-doped CNT (N-CNT) electrodes was investigated and found to obey Langmuir adsorption isotherm characteristics. The amount adsorbed and adsorption maximum are dependent on exposure time, the concentration of adsorbate, and the ionic strength of the solution. The formal potentials measured for FAD and GOx are identical, indicating that the observed electroactivity is from FAD, the redox reaction center of GOx. When glucose is added to GOx adsorbed onto CNT/N-CNT electrodes, direct electron transfer (DET) from enzyme-active FAD is not observed. However, efficient mediated electron transfer (MET) occurs if an appropriate electron mediator is placed in solution, or the natural electron mediator oxygen is used, indicating that GOx is adsorbed and active on CNT/N-CNT electrodes. The observed surface-confined redox reaction at both CNT and N-CNT electrodes is from FAD that either specifically adsorbs from solution or adsorbs from the holoprotein subsequently inactivating the enzyme. The splitting of cathodic and anodic peak potentials as a function of scan rate provides a way to measure the heterogeneous electron-transfer rate constant (k(s)) using Laviron's method. However, the measured k(s) was found to be under ohmic control, not under the kinetic control of an electron-transfer reaction, suggesting that k(s) for FAD on CNTs is faster than the measured value of 7.6 s(-1).

  16. Patterning Method for Silver Nanoparticle Electrodes in Fully Solution-Processed Organic Thin-Film Transistors Using Selectively Treated Hydrophilic and Hydrophobic Surfaces

    NASA Astrophysics Data System (ADS)

    Fukuda, Kenjiro; Takeda, Yasunori; Kobayashi, Yu; Shimizu, Masahiro; Sekine, Tomohito; Kumaki, Daisuke; Kurihara, Masato; Sakamoto, Masatomi; Tokito, Shizuo

    2013-05-01

    Fully solution-processed organic thin-film transistor (OTFT) devices have been fabricated with simple patterning process at a relatively low process temperature of 100 °C. In the patterning process, a hydrophobic amorphous fluoropolymer material, which was used as the gate dielectric layer and the underlying base layer, was treated with an oxygen plasma to selectively change its surface wetting properties from hydrophobic to hydrophilic. Silver source and drain electrodes were successfully formed in the treated areas with highly uniform line widths and without residues between the electrodes. Nonuniformities in the thickness of the silver electrodes originating from the “coffee-ring” effect were suppressed by optimizing the blend of solvents used with the silver nanoparticles, such that the printed electrodes are appropriate for bottom-gate OTFT devices. A fully solution-processed OTFT device using a polymer semiconductor material (PB16TTT) exhibited good electrical performance with no hysteresis in its transfer characteristics and with good linearity in its output characteristics. A relatively high carrier mobility of 0.14 cm2 V-1 s-1 and an on/off ratio of 1×105 were obtained with the fabricated TFT device.

  17. CO (a{sup 3}Π) quenching at a metal surface: Evidence of an electron transfer mediated mechanism

    SciTech Connect

    Grätz, Fabian; Engelhart, Daniel P.; Wagner, Roman J. V.; Wodtke, Alec M.; Schäfer, Tim; Meijer, Gerard

    2014-07-28

    We observe a strong influence of molecular vibration and surface temperature on electron emission promoted by the de-excitation of metastable CO(a{sup 3}Π) on a clean Au(111) surface using a molecular beam surface scattering apparatus. The de-excitation is independent of incidence translational energy. These observations appear incompatible with existing theories of metastable particle de-excitation on metal surfaces, which are based on the Auger effect. Instead, they strongly suggest a mechanism involving formation of a transient anion whose lifetime is similar to the vibrational period of the CO molecule.

  18. Electrode for electrochemical cell

    DOEpatents

    Kaun, T.D.; Nelson, P.A.; Miller, W.E.

    1980-05-09

    An electrode structure for a secondary electrochemical cell includes an outer enclosure defining a compartment containing electrochemical active material. The enclosure includes a rigid electrically conductive metal sheet with perforated openings over major side surfaces. The enclosure can be assembled as first and second trays each with a rigid sheet of perforated electrically conductive metal at major side surfaces and normally extending flanges at parametric margins. The trays can be pressed together with moldable active material between the two to form an expandable electrode. A plurality of positive and negative electrodes thus formed are arranged in an alternating array with porous frangible interelectrode separators within the housing of the secondary electrochemical cell.

  19. Electrode for electrochemical cell

    DOEpatents

    Kaun, Thomas D.; Nelson, Paul A.; Miller, William E.

    1981-01-01

    An electrode structure for a secondary electrochemical cell includes an outer enclosure defining a compartment containing electrochemical active material. The enclosure includes a rigid electrically conductive metal sheet with perforated openings over major side surfaces. The enclosure can be assembled as first and second trays each with a rigid sheet of perforated electrically conductive metal at major side surfaces and normally extending flanges at parametric margins. The trays can be pressed together with moldable active material between the two to form an expandable electrode. A plurality of positive and negative electrodes thus formed are arranged in an alternating array with porous frangible interelectrode separators within the housing of the secondary electrochemical cell.

  20. Laccase immobilization on the electrode surface to design a biosensor for the detection of phenolic compound such as catechol

    NASA Astrophysics Data System (ADS)

    Nazari, Maryam; Kashanian, Soheila; Rafipour, Ronak

    2015-06-01

    Biosensors based on the coupling of a biological entity with a suitable transducer offer an effective route to detect phenolic compounds. Phenol and phenolic compounds are among the most toxic environmental pollutants. Laccases are multi-copper oxidases that can oxide phenol and phenolic compounds. A method is described for construction of an electrochemical biosensor to detect phenolic compounds based on covalent immobilization of laccase (Lac) onto polyaniline (PANI) electrodeposited onto a glassy carbon (GC) electrode via glutaraldehyde coupling. The modified electrode was characterized by voltammetry, Fourier transform infrared (FTIR) spectroscopy and atomic force microscopy (AFM) techniques. The results indicated that laccase was immobilized onto modified GC electrode by the covalent interaction between laccase and terminal functional groups of the glutaraldehyde. The laccase immobilized modified electrode showed a direct electron transfer reaction between laccase and the electrode. Linear range, sensitivity, and detection limit for this biosensor were 3.2 × 10-6 to 19.6 × 10-6 M, 706.7 mA L mol-1, 2.07 × 10-6 M, respectively.

  1. Effects of underpotentially deposited TI and Pb submonolayers on the surface-enhanced Raman scattering (SERS) from pyridine at Ag electrodes

    NASA Astrophysics Data System (ADS)

    Watanabe, T.; Yanagihara, N.; Honda, K.; Pettinger, B.; Moerl, L.

    1983-04-01

    SERS from pyridine on an Ag electrode is almost completely quenched by underpotential deposition of TI to a surface coverage of ≈ 3%. Removal of TI by anodic stripping does not restore the original SERS intensity. These results suggest that only a small fraction of adsorbed pyridine molecules is SERS active, and TI is specifically deposited on such a SERS active site, which then undergoes irreversible destruction. Pb appears to be non-specifically deposited on the Ag surface, but exhibits a similar irreversible quenching of SERS.

  2. Electrostatic-Force-Assisted Dispensing Printing to Construct High-Aspect-Ratio of 0.79 Electrodes on a Textured Surface with Improved Adhesion and Contact Resistivity

    NASA Astrophysics Data System (ADS)

    Shin, Dong-Youn; Yoo, Sung-Soo; Song, Hee-Eun; Tak, Hyowon; Byun, Doyoung

    2015-11-01

    As a novel route to construct fine and abnormally high-aspect-ratio electrodes with excellent adhesion and reduced contact resistivity on a textured surface, an electrostatic-force-assisted dispensing printing technique is reported and compared with conventional dispensing and electrohydrodynamic jet printing techniques. The electrostatic force applied between a silver paste and the textured surface of a crystalline silicon solar cell wafer significantly improves the physical adhesion of the electrodes, whereas those fabricated using a conventional dispensing printing technique peel off with a silver paste containing 2 wt% of a fluorosurfactant. Moreover, the contact resistivity and dimensionless deviation of total resistance are significantly reduced from 2.19 ± 1.53 mΩ·cm2 to 0.98 ± 0.92 mΩ·cm2 and from 0.10 to 0.03, respectively. By utilizing electrodes with an abnormally high-aspect-ratio of 0.79 (the measured thickness and width are 30.4 μm and 38.3 μm, respectively), the cell efficiency is 17.2% on a polycrystalline silicon solar cell with an emitter sheet resistance of 60 Ω/sq. This cell efficiency is considerably higher than previously reported values obtained using a conventional electrohydrodynamic jet printing technique, by +0.48-3.5%p.

  3. Investigation of protein FTT1103 electroactivity using carbon and mercury electrodes. Surface-inhibition approach for disulfide oxidoreductases using silver amalgam powder.

    PubMed

    Večerková, Renata; Hernychová, Lenka; Dobeš, Petr; Vrba, Jiří; Josypčuk, Bohdan; Bartošík, Martin; Vacek, Jan

    2014-06-01

    Recently, it was shown that electrochemical methods can be used for analysis of poorly water-soluble proteins and for study of their structural changes and intermolecular (protein-ligand) interactions. In this study, we focused on complex electrochemical investigation of recombinant protein FTT1103, a disulfide oxidoreductase with structural similarity to well described DsbA proteins. This thioredoxin-like periplasmic lipoprotein plays an important role in virulence of bacteria Francisella tularensis. For electrochemical analyses, adsorptive transfer (ex situ) square-wave voltammetry with pyrolytic graphite electrode, and alternating-current voltammetry and constant-current chronopotentiometric stripping analysis with mercury electrodes, including silver solid amalgam electrode (AgSAE) were used. AgSAE was used in poorly water-soluble protein analysis for the first time. In addition to basic redox, electrocatalytic and adsorption/desorption characterization of FTT1103, electrochemical methods were also used for sensitive determination of the protein at nanomolar level and study of its interaction with surface of AgSA microparticles. Proposed electrochemical protocol and AgSA surface-inhibition approach presented here could be used in future for biochemical studies focused on proteins associated with membranes as well as on those with disulfide oxidoreductase activity.

  4. Electrostatic-Force-Assisted Dispensing Printing to Construct High-Aspect-Ratio of 0.79 Electrodes on a Textured Surface with Improved Adhesion and Contact Resistivity

    PubMed Central

    Shin, Dong-Youn; Yoo, Sung-Soo; Song, Hee-eun; Tak, Hyowon; Byun, Doyoung

    2015-01-01

    As a novel route to construct fine and abnormally high-aspect-ratio electrodes with excellent adhesion and reduced contact resistivity on a textured surface, an electrostatic-force-assisted dispensing printing technique is reported and compared with conventional dispensing and electrohydrodynamic jet printing techniques. The electrostatic force applied between a silver paste and the textured surface of a crystalline silicon solar cell wafer significantly improves the physical adhesion of the electrodes, whereas those fabricated using a conventional dispensing printing technique peel off with a silver paste containing 2 wt% of a fluorosurfactant. Moreover, the contact resistivity and dimensionless deviation of total resistance are significantly reduced from 2.19 ± 1.53 mΩ·cm2 to 0.98 ± 0.92 mΩ·cm2 and from 0.10 to 0.03, respectively. By utilizing electrodes with an abnormally high-aspect-ratio of 0.79 (the measured thickness and width are 30.4 μm and 38.3 μm, respectively), the cell efficiency is 17.2% on a polycrystalline silicon solar cell with an emitter sheet resistance of 60 Ω/sq. This cell efficiency is considerably higher than previously reported values obtained using a conventional electrohydrodynamic jet printing technique, by +0.48–3.5%p. PMID:26576857

  5. Electrocatalytic Reduction of Oxygen on Platinum Nanoparticles in the Presence and Absence of Interactions with the Electrode Surface.

    PubMed

    Ostojic, Nevena; Crooks, Richard M

    2016-09-27

    We report that ultraviolet/ozone (UV/O3) treatment can be used to remove sixth-generation, hydroxyl-terminated poly(amidoamine) (PAMAM) dendrimers from dendrimer-encapsulated Pt nanoparticles (Pt DENs) previously immobilized onto a pyrolyzed photoresist film (PPF) electrode. Results from X-ray photoelectron spectroscopy, scanning transmission electron microscopy, and electrochemical experiments indicate that removal of the dendrimer proceeds without changes to the size, shape, or electrocatalytic properties of the encapsulated nanoparticles. The UV/O3 treatment did not damage the PPF electrode. The electrocatalytic properties of the DENs before and after removal of the dendrimer were nearly identical.

  6. Electrocatalytic Reduction of Oxygen on Platinum Nanoparticles in the Presence and Absence of Interactions with the Electrode Surface.

    PubMed

    Ostojic, Nevena; Crooks, Richard M

    2016-09-27

    We report that ultraviolet/ozone (UV/O3) treatment can be used to remove sixth-generation, hydroxyl-terminated poly(amidoamine) (PAMAM) dendrimers from dendrimer-encapsulated Pt nanoparticles (Pt DENs) previously immobilized onto a pyrolyzed photoresist film (PPF) electrode. Results from X-ray photoelectron spectroscopy, scanning transmission electron microscopy, and electrochemical experiments indicate that removal of the dendrimer proceeds without changes to the size, shape, or electrocatalytic properties of the encapsulated nanoparticles. The UV/O3 treatment did not damage the PPF electrode. The electrocatalytic properties of the DENs before and after removal of the dendrimer were nearly identical. PMID:27641461

  7. Electron transfer between glucose oxidase and electrodes via redox mediators bound with flexible chains to the enzyme surface

    NASA Astrophysics Data System (ADS)

    Heller, Adam; Schuhmann, Wolfgang; Ohara, Timothy J.; Schmidt, Hanns-Ludwig

    1991-01-01

    Electrical communication between redox centers of glucose oxidase and vitreous carbon electrodes is established through binding to oligosaccharides, at the periphery of the enzyme, ferrocene functions pendant on flexible chains. Communication is effective when the chains are long (greater than 10 bonds), but when the chains are short (less than 5 bonds). When attached to long flexible chains the peripherally bound relays penetrate the enzyme to a sufficient depth to reduce the electron transfer distances between a redox center of the enzyme and the relay and between the relay and electrode, thereby increasing the rate of electron transfer.

  8. Surface adhesion and confinement variation of Staphylococcus aurius on SAM surfaces

    NASA Astrophysics Data System (ADS)

    Amroski, Alicia; Olsen, Morgan; Calabrese, Joseph; Senevirathne, Reshani; Senevirathne, Indrajith

    2012-02-01

    Controlled surface adhesion of non - pathogenic gram positive strain, Staphylococcus aureus is interesting as a model system due to possible development of respective biosensors for prevention and detection of the pathogenic strain methicillin resistant Staphylococcus aureus (MRSA) and further as a study for bio-machine interfacing. Self Assembled Monolayers (SAM) with engineered surfaces of linear thiols on Au(111) were used as the substrate. Sub cultured S. aureus were used for the analysis. The SAM layered surfaces were dipped in 2 -- 4 Log/ml S. aureus solution. Subsequent surface adhesion at different bacterial dilutions on surfaces will be discussed, and correlated with quantitative and qualitative adhesion properties of bacteria on the engineered SAM surfaces. The bacteria adhered SAM surfaces were investigated using intermittent contact, noncontact, lateral force and contact modes of Atomic Force Microscopy (AFM).

  9. Symmetry superposition studied by surface second-harmonic generation

    NASA Astrophysics Data System (ADS)

    Lüpke, G.; Marowsky, G.; Steinhoff, R.; Friedrich, A.; Pettinger, B.; Kolb, D. M.

    1990-04-01

    The components of a third-rank χ(2) tensor have been split into contributions due to 1-fold, 2-fold, 3-fold, and ∞-fold or isotropic rotation axes for a surface of Cs symmetry. Theoretical analysis of the rotation patterns obtained by the surface second-harmonic (SH) generation indicates that a complete symmetry analysis cannot be performed without knowledge of the relevant distribution functions. Rotation axes of lower symmetry create via ``overtones'' or ``harmonics'' contributions apparent in the analysis of the rotation axes of higher symmetry. An experimental example is the observation of structural changes of Au(111) surfaces in an aqueous electrolytic environment. Potential-dependent buildup and removal of a Au(111)-(1×23) surface could be monitored in situ and in real time. Symmetry analysis of the SH rotation patterns reveals both contributions due to a 3-fold axis due to the regular (1×1) structure and simultaneously a 1-fold and a 2-fold axis due to the (1×23) reconstruction.

  10. Electrode compositions

    DOEpatents

    Block, Jacob; Fan, Xiyun

    1998-01-01

    An electrode composition for use as an electrode in a non-aqueous battery system. The electrode composition contains an electrically active powder in a solid polymer and, as a dispersant, a C.sub.8 -C.sub.15 alkyl capped oligomer of a hexanoic acid that is electrochemically inert at 2.5-4.5 volts.

  11. Electrode compositions

    DOEpatents

    Block, J.; Fan, X.

    1998-10-27

    An electrode composition is described for use as an electrode in a non-aqueous battery system. The electrode composition contains an electrically active powder in a solid polymer and, as a dispersant, a C{sub 8}-C{sub 15} alkyl capped oligomer of a hexanoic acid that is electrochemically inert at 2.5--4.5 volts.

  12. Surface-enhanced resonance Raman scattering from methylviologen at a silver electrode: Evidence for two distinct adsorption interactions

    SciTech Connect

    Feng, Qiao; Yue, W.; Cotton, T.M. )

    1990-03-08

    The electronic absorption and resonance Raman spectra of methylviologen radical cation (MV{sup {sm bullet}+}) and fully reduced methylviologen (MV{sup 0}) have been characterized. The enhancement of Raman and resonance Raman (RR) scattering from the dication and its reduction products at polished and roughened silver electrodes was also investigated.

  13. Bifunctional catalytic electrode

    NASA Technical Reports Server (NTRS)

    Cisar, Alan (Inventor); Murphy, Oliver J. (Inventor); Clarke, Eric (Inventor)

    2005-01-01

    The present invention relates to an oxygen electrode for a unitized regenerative hydrogen-oxygen fuel cell and the unitized regenerative fuel cell having the oxygen electrode. The oxygen electrode contains components electrocatalytically active for the evolution of oxygen from water and the reduction of oxygen to water, and has a structure that supports the flow of both water and gases between the catalytically active surface and a flow field or electrode chamber for bulk flow of the fluids. The electrode has an electrocatalyst layer and a diffusion backing layer interspersed with hydrophilic and hydrophobic regions. The diffusion backing layer consists of a metal core having gas diffusion structures bonded to the metal core.

  14. Electrodes for microfluidic applications

    DOEpatents

    Crocker, Robert W.; Harnett, Cindy K.; Rognlien, Judith L.

    2006-08-22

    An electrode device for high pressure applications. These electrodes, designed to withstand pressure of greater than 10,000 psi, are adapted for use in microfluidic devices that employ electrokinetic or electrophoretic flow. The electrode is composed, generally, of an outer electrically insulating tubular body having a porous ceramic frit material disposed in one end of the outer body. The pores of the porous ceramic material are filled with an ion conductive polymer resin. A conductive material situated on the upper surface of the porous ceramic frit material and, thus isolated from direct contact with the electrolyte, forms a gas diffusion electrode. A metal current collector, in contact with the gas diffusion electrode, provides connection to a voltage source.

  15. Surface Acoustic Wave Duplexer Composed of SiO2/Cu Electrode/LiNbO3 Structure Having Convex and Concave Portions

    NASA Astrophysics Data System (ADS)

    Nakai, Yasuharu; Nakao, Takeshi; Nishiyama, Kenji; Kadota, Michio

    2009-07-01

    The transition bandwidth of 20 MHz between the transmission (Tx: 1850-1910 MHz) and the receiving (Rx: 1930-1990 MHz) bands of personal communication service (PCS) handy phones in the United States (US) is very narrow compared with those of other systems. We have already realized surface acoustic wave (SAW) duplexers with sizes of 5.0×5.0×1.7 and 3.0×2.5×1.2 mm3 for PCS handy phones in the US with an excellent temperature coefficient of frequency (TCF) by using a shear horizontal (SH) wave on a flattened SiO2/Cu electrode/36-48° YX-LiTaO3 structure and a Rayleigh wave on a SiO2/Cu electrode/120-128° YX-LiNbO3 structure. Although the surface of the above-mentioned structures is flattened SiO2, we have also studied the shape of the SiO2 surface. As a result, in addition to increasing the stop-band width, which corresponds to the reflection coefficient, the TCF and power durability have been improved by forming convex portions on the surface of the SiO2 over the interdigital transducer (IDT) gaps.

  16. Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces

    NASA Astrophysics Data System (ADS)

    Murphy, Colin J.; Carrasco, Javier; Lawton, Timothy J.; Liriano, Melissa L.; Baber, Ashleigh E.; Lewis, Emily A.; Michaelides, Angelos; Sykes, E. Charles H.

    2014-07-01

    Methanol is a versatile chemical feedstock, fuel source, and energy storage material. Many reactions involving methanol are catalyzed by transition metal surfaces, on which hydrogen-bonded methanol overlayers form. As with water, the structure of these overlayers is expected to depend on a delicate balance of hydrogen bonding and adsorbate-substrate bonding. In contrast to water, however, relatively little is known about the structures methanol overlayers form and how these vary from one substrate to another. To address this issue, herein we analyze the hydrogen bonded networks that methanol forms as a function of coverage on three catalytically important surfaces, Au(111), Cu(111), and Pt(111), using a combination of scanning tunneling microscopy and density functional theory. We investigate the effect of intermolecular interactions, surface coverage, and adsorption energies on molecular assembly and compare the results to more widely studied water networks on the same surfaces. Two main factors are shown to direct the structure of methanol on the surfaces studied: the surface coverage and the competition between the methanol-methanol and methanol-surface interactions. Additionally, we report a new chiral form of buckled hexamer formed by surface bound methanol that maximizes the interactions between methanol monomers by sacrificing interactions with the surface. These results serve as a direct comparison of interaction strength, assembly, and chirality of methanol networks on Au(111), Cu(111), and Pt(111) which are catalytically relevant for methanol oxidation, steam reforming, and direct methanol fuel cells.

  17. Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces.

    PubMed

    Murphy, Colin J; Carrasco, Javier; Lawton, Timothy J; Liriano, Melissa L; Baber, Ashleigh E; Lewis, Emily A; Michaelides, Angelos; Sykes, E Charles H

    2014-07-01

    Methanol is a versatile chemical feedstock, fuel source, and energy storage material. Many reactions involving methanol are catalyzed by transition metal surfaces, on which hydrogen-bonded methanol overlayers form. As with water, the structure of these overlayers is expected to depend on a delicate balance of hydrogen bonding and adsorbate-substrate bonding. In contrast to water, however, relatively little is known about the structures methanol overlayers form and how these vary from one substrate to another. To address this issue, herein we analyze the hydrogen bonded networks that methanol forms as a function of coverage on three catalytically important surfaces, Au(111), Cu(111), and Pt(111), using a combination of scanning tunneling microscopy and density functional theory. We investigate the effect of intermolecular interactions, surface coverage, and adsorption energies on molecular assembly and compare the results to more widely studied water networks on the same surfaces. Two main factors are shown to direct the structure of methanol on the surfaces studied: the surface coverage and the competition between the methanol-methanol and methanol-surface interactions. Additionally, we report a new chiral form of buckled hexamer formed by surface bound methanol that maximizes the interactions between methanol monomers by sacrificing interactions with the surface. These results serve as a direct comparison of interaction strength, assembly, and chirality of methanol networks on Au(111), Cu(111), and Pt(111) which are catalytically relevant for methanol oxidation, steam reforming, and direct methanol fuel cells.

  18. Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces.

    PubMed

    Murphy, Colin J; Carrasco, Javier; Lawton, Timothy J; Liriano, Melissa L; Baber, Ashleigh E; Lewis, Emily A; Michaelides, Angelos; Sykes, E Charles H

    2014-07-01

    Methanol is a versatile chemical feedstock, fuel source, and energy storage material. Many reactions involving methanol are catalyzed by transition metal surfaces, on which hydrogen-bonded methanol overlayers form. As with water, the structure of these overlayers is expected to depend on a delicate balance of hydrogen bonding and adsorbate-substrate bonding. In contrast to water, however, relatively little is known about the structures methanol overlayers form and how these vary from one substrate to another. To address this issue, herein we analyze the hydrogen bonded networks that methanol forms as a function of coverage on three catalytically important surfaces, Au(111), Cu(111), and Pt(111), using a combination of scanning tunneling microscopy and density functional theory. We investigate the effect of intermolecular interactions, surface coverage, and adsorption energies on molecular assembly and compare the results to more widely studied water networks on the same surfaces. Two main factors are shown to direct the structure of methanol on the surfaces studied: the surface coverage and the competition between the methanol-methanol and methanol-surface interactions. Additionally, we report a new chiral form of buckled hexamer formed by surface bound methanol that maximizes the interactions between methanol monomers by sacrificing interactions with the surface. These results serve as a direct comparison of interaction strength, assembly, and chirality of methanol networks on Au(111), Cu(111), and Pt(111) which are catalytically relevant for methanol oxidation, steam reforming, and direct methanol fuel cells. PMID:25005297

  19. Exchange interaction of strongly anisotropic tripodal erbium single-ion magnets with metallic surfaces.

    PubMed

    Dreiser, Jan; Wäckerlin, Christian; Ali, Md Ehesan; Piamonteze, Cinthia; Donati, Fabio; Singha, Aparajita; Pedersen, Kasper Steen; Rusponi, Stefano; Bendix, Jesper; Oppeneer, Peter M; Jung, Thomas A; Brune, Harald

    2014-05-27

    We present a comprehensive study of Er(trensal) single-ion magnets deposited in ultrahigh vacuum onto metallic surfaces. X-ray photoelectron spectroscopy reveals that the molecular structure is preserved after sublimation, and that the molecules are physisorbed on Au(111) while they are chemisorbed on a Ni thin film on Cu(100) single-crystalline surfaces. X-ray magnetic circular dichroism (XMCD) measurements performed on Au(111) samples covered with molecular monolayers held at temperatures down to 4 K suggest that the easy axes of the strongly anisotropic molecules are randomly oriented. Furthermore XMCD indicates a weak antiferromagnetic exchange coupling between the single-ion magnets and the ferromagnetic Ni/Cu(100) substrate. For the latter case, spin-Hamiltonian fits to the XMCD M(H) suggest a significant structural distortion of the molecules. Scanning tunneling microscopy reveals that the molecules are mobile on Au(111) at room temperature, whereas they are more strongly attached on Ni/Cu(100). X-ray photoelectron spectroscopy results provide evidence for the chemical bonding between Er(trensal) molecules and the Ni substrate. Density functional theory calculations support these findings and, in addition, reveal the most stable adsorption configuration on Ni/Cu(100) as well as the Ni-Er exchange path. Our study suggests that the magnetic moment of Er(trensal) can be stabilized via suppression of quantum tunneling of magnetization by exchange coupling to the Ni surface atoms. Moreover, it opens up pathways toward optical addressing of surface-deposited single-ion magnets.

  20. Model for calculating low-current moderate-pressure RF discharges with photon-driven secondary electron photoemission from the electrode surface

    SciTech Connect

    Baranov, I. Ya.; Koptev, A. V.

    2007-01-15

    A model is developed for calculating a low-current moderate-pressure RF discharge with allowance for an electron cloud that is formed by electrons produced during the preceding periods of the RF field and fills the electrode sheath at regular intervals in accordance with the phase of the RF voltage applied to the electrodes. The cloud arises due to a phase shift of {pi}/2 between the voltage across the sheath and that across the column of a low-current RF discharge plasma. The photon generation mechanism is as follows: as the cloud electrons fill the sheath, they acquire energy in superelastic collisions with metastables produced by the sheath electrons during the preceding periods of the RF field and then excite the metastable states to emitting levels. The discharge sheath forms due to the overlap of the secondary electron avalanches triggered by electron photoemission from the electrode surface. The parameters of the sheath in a low-current RF discharge are determined by the conditions under which the electron photoemission current in the sheath is self-sustaining, but the capacitive susceptance of the sheath is substantially higher than its active electrical conductance. The results of calculations are compared with the experimental data.