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Sample records for au111 electrode surfaces

  1. 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. PMID:27001527

  2. Correction: 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

    Correction for 'Shell-isolated nanoparticle-enhanced Raman spectroscopy study of the adsorption behaviour of DNA bases on Au(111) electrode surfaces' by Bao-Ying Wen et al., Analyst, 2016, DOI: 10.1039/c6an00180g. PMID:27082242

  3. Interaction of HNCO with Au(111) surfaces

    NASA Astrophysics Data System (ADS)

    Farkas, A. P.; Berkó, A.; Solymosi, F.

    2012-08-01

    The surface chemistry of isocyanic acid, HNCO, and its dissociation product, NCO, was studied on clean, O-dosed and Ar ion bombarded Au(111) surfaces. The techniques used are high resolution energy loss spectroscopy (HREELS) and temperature-programmed desorption (TPD). The structure of Ar ion etched surface is explored by scanning tunneling microscopy (STM). HNCO adsorbs molecularly on Au(111) surface at 100 K yielding strong losses at 1390, 2270 and 3230 cm- 1. The weakly adsorbed HNCO desorbs in two peaks characterized by Tp = 130 and 145 K. The dissociation of the chemisorbed HNCO occurs at 150 K to give NCO species characterized by a vibration at 2185 cm- 1. The dissociation process is facilitated by the presence of preadsorbed O and by defect sites on Au(111) produced by Ar ion bombardment. In the latter case the loss feature of NCO appeared at 2130 cm- 1. Isocyanate on Au(111) surface was found to be more stable than on the single crystal surfaces of Pt-group metals. Results are compared with those obtained on supported Au catalysts.

  4. Electrodeposited bismuth monolayers on Au(111) electrodes. Comparison of surface X-ray scattering, scanning tunneling microscopy, and atomic force microscopy lattice structures

    SciTech Connect

    Chen, C.H.; Kepler, K.D.; Gewirth, A.A. ); Ocko, B.M.; Wang, J. )

    1993-07-15

    Surface X-ray scattering (SXS) and scanning tunneling microscope (STM) studies have been carried out to determine the structure of electrochemically deposited Bi monolayers on a Au(111) electrode. Between 10 and 190 mV (relative to bulk deposition), a uniaxially commensurate rectangular phase is formed in which the Bi coverage decreases from 0.646 to 0.616 relative to a gold monolayer. A 25% coverage (2 [times] 2) phase is stable between 200 and 280 mV. The structures determined by SXS and STM are in agreement with those determined previously by AFM. 15 refs., 5 figs.

  5. In situ real-time study on potential induced structure change at Au(111) and Au(100) single crystal electrode/sulfuric acid solution interfaces by surface x-ray scattering

    NASA Astrophysics Data System (ADS)

    Kondo, Toshihiro; Zegenhagen, Jörg; Takakusagi, Satoru; Uosaki, Kohei

    2015-01-01

    Surface X-ray scattering (SXS) measurements were carried out to monitor the potential induced structure changes such as surface reconstruction lifting, adsorption of oxygen species, formation of surface oxide bilayer, reduction of surface oxide, and surface reconstruction at Au(111)/H2SO4 and Au(100)/H2SO4 interfaces in situ in real time using intense high energy X-ray. The phase transition of the reconstruction/lifting, adsorption of oxygen species, and surface oxide formation/reduction at the Au(100) electrode proceed much slower, slightly slower, and faster, respectively, than at the Au(111) electrode.

  6. Potential-step chronocoulometric investigation of the surface coverages of coadsorbed Bi and hydroxide on Au(111) electrodes

    SciTech Connect

    Niece, B.K.; Gewirth, A.A.

    1996-10-02

    Bi underpotentially deposited on Au(111) has been studied using potential-step chronocoulometry to determine the actual surface coverage of Bi. In the potential region where this system exhibits catalytic activity for the electroreduction of peroxide to water, the observed coverage is 0.25 monolayer (ML), which agrees well with the coverage of the reported (2 x 2) Bi overlayer observed by scanning probe microscopy in this region. At more cathodic potentials, the coverage increases to 0.67 ML. This coverage agrees with the expected based on the (p x {radical}3) structure proposed from scanning tunneling microscopy, atomic force microscopy, and SXS measurements in this region. The electrosorption valency calculated based on these coverages is 3, indicating that the Bi is fully discharged on the surface. Potential-step chronocoulometry has been used at various pH values to determine the surface coverage of hydroxide anion in the presence of underpotentially deposited (upd) Bi. The coverage is negligible in the absence of upd Bi and at potentials where the Bi adlayer condenses. It rises to a peak of 0.17 ML in the region where the coverage is 0.25 ML, indicating that OH{sup -} is coadsorbed with the Bi. 30 refs., 10 figs.

  7. Do Methanethiol Adsorbates on the Au(111) Surface Dissociate?

    NASA Astrophysics Data System (ADS)

    Zhou, Jian-Ge; Hagelberg, Frank

    2006-07-01

    The interaction of methanethiol molecules CH3SH with the Au(111) surface is investigated, and it is found for the first time that the S-H bond remains intact when the methanethiol molecules are adsorbed on the regular Au(111) surface. However, it breaks if defects are present in the Au(111) surface. At low coverage, the fcc region is favored for S atom adsorption, but at saturated coverage the adsorption energies at various sites are almost isoenergetic. The presented calculations show that a methanethiol layer on the regular Au(111) surface does not dimerize.

  8. 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.

  9. 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. PMID:16534826

  10. Chlorine adsorption on Au(111): chlorine overlayer or surface chloride?

    PubMed

    Gao, Weiwei; Baker, Thomas A; Zhou, Ling; Pinnaduwage, Dilini S; Kaxiras, Efthimios; Friend, Cynthia M

    2008-03-19

    We report the first scanning tunneling microscope (STM) investigation, combined with density functional theory calculations, to resolve controversy regarding the bonding and structure of chlorine adsorbed on Au(111). STM experiments are carried out at 120 K to overcome instability caused by mobile species upon chlorine adsorption at room temperature. Chlorine adsorption initially lifts the herringbone reconstruction. At low coverages (<0.33 ML), chlorine binds to the top of Au(111)-(1 x 1) surface and leads to formation of an overlayer with (square root(3) x square root(3))R30 degree structure at 0.33 ML. At higher coverages, packing chlorine into an overlayer structure is no longer favored. Gold atoms incorporate into a complex superlattice of a Au-Cl surface compound. PMID:18290645

  11. Building chessboard-like supramolecular structures on Au(111) surfaces.

    PubMed

    Dou, Ruifen; Yang, Yu; Zhang, Ping; Zhong, Dingyong; Fuchs, Harald; Wang, Yue; Chi, Lifeng

    2015-09-25

    We investigate an anthracene derivative, 3(5)-(9-anthryl) pyrazole (ANP), self-assembled on the Au(111) surface by means of scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. A chessboard-like network structure composed of ANP molecules is found, covering the whole Au(111) substrate. Our STM results and DFT calculations reveal that the formation of chessboard-like networks originates from a basic unit cell, a tetramer structure, which is formed by four ANP molecules connected through C-H…N hydrogen bonds. The hydrogen bonds inside each tetramer and the molecule-substrate interaction are fundamentally important in providing a driving force for formation of the supramolecular networks. PMID:26314756

  12. Building chessboard-like supramolecular structures on Au(111) surfaces

    NASA Astrophysics Data System (ADS)

    Dou, Ruifen; Yang, Yu; Zhang, Ping; Zhong, Dingyong; Fuchs, Harald; Wang, Yue; Chi, Lifeng

    2015-09-01

    We investigate an anthracene derivative, 3(5)-(9-anthryl) pyrazole (ANP), self-assembled on the Au(111) surface by means of scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. A chessboard-like network structure composed of ANP molecules is found, covering the whole Au(111) substrate. Our STM results and DFT calculations reveal that the formation of chessboard-like networks originates from a basic unit cell, a tetramer structure, which is formed by four ANP molecules connected through C-H…N hydrogen bonds. The hydrogen bonds inside each tetramer and the molecule-substrate interaction are fundamentally important in providing a driving force for formation of the supramolecular networks.

  13. 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

  14. 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.

  15. Surface charge--induced ordering of the au(111) surface.

    PubMed

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

    1992-03-13

    Synchrotron surface x-ray scattering (SXS) studies have been carried out at the Au(lll)/electrolyte interface to determine the influence of surface charge on the microscopic arrangement of gold surface atoms. At the electrochemical interface, the surface charge density can be continuously varied by controlling the applied potential. The top layer of gold atoms undergoes a reversible phase transition between the (1 x 1) bulk termination and a (23 x radical3) reconstructed phase on changing the electrode potential. In order to differentiate the respective roles of surface charge and adsorbates, studies were carried out in 0.1 M NaF, NaCl, and NaBr solutions. The phase transition occurs at an induced surface charge density of 0.07 +/- 0.02 electron per atom in all three solutions. PMID:17801231

  16. Adsorption Structures and Electronic Properties of 1,4-Phenylene Diisocyanide on the Au(111) Surface

    SciTech Connect

    White, M.G.; Zhou, J.; Acharya, D.; Camillone III, N.; Sutter, P.

    2011-01-10

    The adsorption structures and electronic properties of 1,4-phenylene diisocyanide (PDI) on a Au(111) surface have been studied using temperature programmed desorption (TPD), two-photon photoemission (2PPE), and scanning tunneling microscopy (STM). As deposited at 95 K, PDI molecules form disordered islands and short one-dimensional chains on Au(111) terraces. The work function decreases with increasing PDI coverage, and an occupied electronic state appears at 0.88 eV below the Fermi level. Annealing to 300 K causes the PDI molecules to reorganize on the surface and form ordered, one-dimensional molecular chains that extend for many tens of nanometers across the Au(111) terraces. The repeating structure of the molecular chains is consistent with a recently proposed [-Au-PDI-]{sub n} structure in which PDI molecules lie parallel to the surface and are interconnected by Au adatoms released from the Au(111) surface. The formation of the molecular chains is accompanied by a large drop in the work function which we attribute to an increase in the number and magnitude of interfacial dipoles. The electronic structure of the molecular chains is also characterized by occupied and unoccupied states at -0.88 eV below and +3.32 eV above the Fermi level, respectively. The latter are most prominent after annealing a PDI/Au(111) surface to 300 K, indicating that they are associated with interfacial states of the one-dimensional molecular chains.

  17. Headgroup dimerization in methanethiol monolayers on the Au(111) surface: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Zhou, Jian-Ge; Williams, Quinton L.; Hagelberg, Frank

    2007-08-01

    A long-standing controversy related to the dimer pattern formed by S atoms in methanethiol (CH3SH) on the Au(111) surface has been resolved using density functional theory. Here, dimerization of methanethiol adsorbates on the Au(111) surface is established by computational modeling. For methylthiolate (CH3S) , it is shown that the S atoms do not dimerize at high coverage but reveal a dimer pattern at intermediate coverage. Molecular dynamics simulation at high coverage demonstrates that the observed dialkyl disulfide species are formed during the desorption process, and thus are not attached to the surface.

  18. 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.

  19. PM-IRRAS Studies of DMPC Bilayers Supported on Au(111) Electrodes Modified with Hydrophilic Monolayers of Thioglucose.

    PubMed

    Matyszewska, Dorota; Bilewicz, Renata; Su, ZhangFei; Abbasi, Fatemah; Leitch, J Jay; Lipkowski, Jacek

    2016-02-23

    A phospholipid bilayer composed of 1,2-dimyristoyl-d54-sn-glycero-3-phosphocholine (d54-DMPC) was deposited onto the Au(111) electrode modified with a self-assembled monolayer of 1-thio-β-d-glucose (β-Tg) via the Langmuir-Blodgett and Langmuir-Schaefer (LB-LS) techniques. Polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) measurements were used to characterize structural and orientational changes in this model biological membrane on a hydrophilic surface modified gold electrode. The results of the spectroscopic measurements showed that the tilt angle of acyl chains obtained for deuterated DMPC bilayers supported on the β-Tg-modified gold is significantly lower than that reported previously for DMPC bilayers deposited directly on Au(111) electrodes. Moreover, tilt angles of ∼18° were obtained for d54-DMPC bilayers on β-Tg self-assembled monolayers (SAMs) at positive potentials, which are similar to the values calculated for h-DMPC deposited on bare gold in the desorbed state and to those observed for a stack of hydrated DMPC bilayers. This data confirms that the β-thioglucose SAM promotes the formation of a water cushion that separates the phospholipid bilayer from the metal surface. As a result, the DMPC polar heads are not in direct contact with the electrode and can adopt a zigzag configuration, which strengthens the chain-chain interactions and allows for an overall decrease in the tilt of the acyl chains. These novel supported model membranes may be especially useful in studies pertaining to the incorporation of peptides and proteins into phospholipid bilayers. PMID:26829620

  20. Self-Assembly of Thiol Adsorbates on the Au(111)surface

    NASA Astrophysics Data System (ADS)

    Hagelberg, Frank; Williams, Quinton; Zhou, Jian-Ge

    2007-03-01

    A long-standing controversy related to the dimer pattern formed by methanethiol (CH3SH) and methylthiolate (CH3S) on the Au(111) surface has been resolved using density functional theory within periodic boundary conditions. It is found that the S atoms of methanethiol adsorbates on the Au(111) surface form Van der Waals dimers. For methylthiolate, it is shown that no dimerization occurs at high coverage. At intermediate coverage, however, a Van der Waals dimer pattern emerges. The presence of defects in the Au(111) surface does not change this conclusion. Molecular dynamics simulation at high coverage demonstrates that the observed dialkyl disulfide species emerge during the desorption process, and thus are not attached to the surface. A meta-stable monomer pattern has been shown to be only marginally higher in adsorption energy than the dimer configuration which explains the observed fragility of the dimers. For the understanding of these results, it is of crucial importance that methanethiol molecules, contrary to a widely held assumption, remain stable when deposited on clean Au(111) surfaces /1, 2/. In the presence of defects, however, methanethiol adsorbates dissociate and form methylthiolate. /1/ I. Rzeznicka, J. Lee, P. Maksymovych, J. Yates, Jr., J. Phys. Chem. B109, 15992 (2005). /2/ J. Zhou, F. Hagelberg, Phys. Rev. Lett. 97, 45505 (2006).

  1. 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.

  2. Gold-Adatom-Mediated Bonding in Self-Assembled Short-Chain Alkanethiolate Species on the Au(111) Surface

    SciTech Connect

    Maksymovych, P.; Sorescu, D.C.; Yates, J.T., Jr.

    2006-10-06

    Microscopic evidence for Au-adatom-induced self-assembly of alkanethiolate species on the Au(111) surface is presented. Based on STM measurements and density-functional theory calculations, a new model for the low-coverage self-assembled monolayer of alkanethiolate on the Au(111) surface is developed, which involves the adsorbate complexes incorporating Au adatoms. It is also concluded that the Au(111) herringbone reconstruction is lifted by the alkanethiolate self-assembly because the reconstructed surface layer provides reactive Au adatoms that drive self-assembly.

  3. Self-assembly of methanethiol on the reconstructed Au(111) surface

    NASA Astrophysics Data System (ADS)

    Nenchev, Georgi; Diaconescu, Bogdan; Hagelberg, Frank; Pohl, Karsten

    2009-08-01

    We present a combined experimental and theoretical study of molecular methanethiol (CH3SH) adsorption on the reconstructed Au(111) surface in the temperature range between 90 and 300 K in UHV. We find that the simplest thiol molecules form two stable self-assembled monolayer (SAM) structures that are created by distinct processes. Below 120 K, a solid rectangular phase, preserving the herringbone reconstruction, emerges from individual chains of spontaneously formed dimers. At higher adsorption temperatures below 170 K, a close-packed phase forms via dissociative CH3SH adsorption and the formation of Au adatoms that are not incorporated into the SAM. We show that the combination of a strong substrate-mediated interaction with nondissociative dimerization and temperature activated removal of the Au(111) reconstruction drives the large-scale assembly of molecular CH3SH into two distinct phases.

  4. Synthesis of TiO2 Nanoparticles on the Au(111) Surface

    SciTech Connect

    Biener, J; Farfan-Arribas, E; Biener, M M; Friend, C M; Madix, R J

    2005-01-11

    The growth of titanium oxide nanoparticles on reconstructed Au(111) surfaces was investigated by scanning tunneling microscopy and X-ray photoelectron spectroscopy. Ti was deposited by physical vapor deposition at 300 K. Regular arrays of titanium nanoparticles form by preferential nucleation of Ti at the elbow sites of the herringbone reconstruction. Titanium oxide clusters were synthesized by subsequent exposure to O{sub 2} at 300 K. Two- and three-dimensional titanium oxide nanocrystallites form during annealing in the temperature range from 600 to 900 K. At the same time, the Au(111) surface assumes a serrated, <110> oriented step-edge morphology, suggesting step-edge pinning by titanium oxide nanoparticles. The oxidation state of these titanium oxide nanoparticles varies with annealing temperature. Specifically, annealing to 900 K results in the formation of stoichiometric TiO{sub 2} nanocrystals as judged by the observed XPS binding energies. Nano-dispersed TiO{sub 2} on Au(111) is an ideal system to test the various models explaining the enhanced catalytic reactivity of supported Au nanoparticles.

  5. Snapshots of crystal growth. Nanoclusters of organic conductors on Au(111) surfaces

    SciTech Connect

    Schott, J.H.; Ward, M.D. )

    1994-07-27

    Mono- and multilayer crystalline nanoclusters of tetrathiafulvalene-tetracyanoquinodimethane (TTF)-(TCNQ), a low-dimensional organic conductor in the bulk form, can be formed readily on Au(111) surfaces by vapor phase sublimation under ambient conditions. Scanning tunneling microscopy of monolayer (TTF)(TCNQ) films reveals a two-dimensional density of states (DOS) that is consistent with the arrangement of TTF and TCNQ molecules in the ac face of bulk (TTF)(TCNQ), in which the molecular planes are nearly parallel to the Au(111) substrate. In contrast, clusters with thicknesses corresponding to two or three molecular layers exhibit a transformation to a highly anisotropic DOS that can be attributed to interlayer molecular overlap in segregated TTF and TCNQ molecular chains along the c axis, which can be described as molecular wires'. The orientation of the crystalline (TTF)(TCNQ) clusters is preserved throughout the crystal growth sequence, leading to meso- and macroscopic (TTF)(TCNQ) needles that are oriented perpendicular to the Au(111) substrate. 23 refs., 4 figs.

  6. Intermolecular interactions and substrate effects for an adamantane monolayer on a Au(111) surface

    NASA Astrophysics Data System (ADS)

    Sakai, Yuki; Nguyen, Giang D.; Capaz, Rodrigo B.; Coh, Sinisa; Pechenezhskiy, Ivan V.; Hong, Xiaoping; Wang, Feng; Crommie, Michael F.; Saito, Susumu; Louie, Steven G.; Cohen, Marvin L.

    2013-12-01

    We study theoretically and experimentally the infrared (IR) spectrum of an adamantane monolayer on a Au(111) surface. Using a STM-based IR spectroscopy technique (IRSTM) we are able to measure both the nanoscale structure of an adamantane monolayer on Au(111) as well as its infrared spectrum, while DFT-based ab initio calculations allow us to interpret the microscopic vibrational dynamics revealed by our measurements. We find that the IR spectrum of an adamantane monolayer on Au(111) is substantially modified with respect to the gas-phase IR spectrum. The first modification is caused by the adamantane-adamantane interaction due to monolayer packing, and it reduces the IR intensity of the 2912 cm-1 peak (gas phase) by a factor of 3.5. The second modification originates from the adamantane-gold interaction, and it increases the IR intensity of the 2938 cm-1 peak (gas phase) by a factor of 2.6 and reduces its frequency by 276 cm-1. We expect that the techniques described here can be used for an independent estimate of substrate effects and intermolecular interactions in other diamondoid molecules and for other metallic substrates.

  7. Self-assembled monolayers of methylselenolate on the Au(111) surface: A combined STM and DFT study

    NASA Astrophysics Data System (ADS)

    El-Kareh, L.; Mehring, P.; Caciuc, V.; Atodiresei, N.; Beimborn, A.; Blügel, S.; Westphal, C.

    2014-01-01

    In this study scanning tunneling microscopy (STM) and density functional theory (DFT) were used to investigate the structural formation of methylselenolate (CH3Se) self-assembled monolayers (SAMs) on the Au(111) surface. SAMs were prepared by two different methods, from solution and by exposing the Au(111) surface to gaseous dimethyldiselenide (DMDSe). For methylselenolate (MSe) on the Au(111) surface, our STM measurements revealed the presence of (4 × √3) and (3 × 2√3) rectangular striped phases. These structures were verified by DFT calculations. For both phases, the DFT calculations clearly found a bridge adsorption geometry for MSe on Au(111). Furthermore, they provide information about the electronic structure of the MSe-SAMs.

  8. 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}.

  9. 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.

  10. 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. PMID:27040121

  11. 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.

  12. 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.

  13. Scanning tunneling microscopy study of α,ω-dihexylsexithiophene adlayers on Au(111): a chiral separation induced by a surface.

    PubMed

    Song, Yonghai; Wang, Yu; Wan, Lingli; Ye, Shuhong; Hou, Haoqing; Wang, Li

    2012-08-01

    The self-assembly of α,ω-dihexylsexithiophene molecules on an Au(111) surface was examined by using scanning tunneling microscopy at room temperature, revealing the internal molecular structures of the sexithiophene backbones and the hexyl side chains. The α,ω-dihexylsexithiophene formed a large and well-ordered monolayer in which the molecule lay flatly on the Au(111) surface and was separated into two chiral domains. A detailed observation reveals that the admolecules were packed in one lamellae with their molecular axis aligned along the main axis of the Au(111) substrate with their hexyl chains deviated from <110> direction of the Au(111) substrate by 12 ± 0.5°. In contrast to the behavior in the three-dimensional bulk structure, flat-lying adsorption introduced molecular chirality: right- and left-handed molecules separate into domains of two different orientations, which are mirror symmetric with respect to the <121> direction of the Au(111) substrate. Details of the adlayer structure and the chiral self-assembly were discussed here. PMID:22849803

  14. 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.

  15. 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

  16. 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.

  17. Selective electronalysis of peracetic acid in the presence of a large excess of H2O2 at Au(111)-like gold electrode.

    PubMed

    Awad, M I

    2012-06-12

    Peracetic acid (PAA) has been selectively electroanalyzed in the presence of a large excess of hydrogen peroxide (H(2)O(2)), about 500 fold that of PAA, using Au (111)-like gold electrode in acetate buffer solutions of pH 5.4. Au(111)-like gold electrode was prepared by a controlled reductive desorption of a previously assembled thiol, typically cysteine, monolayer onto the polycrystalline gold (poly-Au) electrode. Cysteine molecules were selectively removed from the Au(111) facets of the poly-Au electrode, keeping the other two facets (i.e., Au(110) and Au(100)) under the protection of the adsorbed cysteine. It has been found that Au(111)-like gold electrode positively shifts the reduction peak of PAA, while, fortunately, shifts the reduction peak of H(2)O(2) negatively, achieving a large potential separation (around 750 mV) between the two reduction peaks as compared with that (around 450 mV) obtained at the poly-Au electrode. This large potential separation between the two reduction peaks enabled the analysis of PAA in the presence of a large excess of H(2)O(2). In addition, the positive shift of the reduction peak of PAA gives the present method a high immunity against the interference of the dissolved oxygen. PMID:22632045

  18. 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

  19. First-principles Investigation of the Stability of Surface Gold Oxides on Au(111)

    NASA Astrophysics Data System (ADS)

    Shi, Hongqing; Stampfl, Catherine

    2006-03-01

    In contrast to the long held view that gold is catalytically inert and as such uninteresting, it is now well known that Au is significantly more active than Pt in the catalytic oxidation of CO under basic environments. Au can also promote many other reactions in the form of nanoparticles on metal oxide and activated carbon supports [1].^ This has simulated huge efforts in an attempt to understand the mechanisms responsible for the high activity, including investigations into the nature of oxygen on gold surfaces [2]. In the present work we have investigated the relative stability of oxygen adsorbed on and under the Au(111) surface, as well as thin surface oxides. We identify structures in which the binding of atomic oxygen is stronger than that at under-coordinated surface Au atoms (e.g. at steps). To determine the stability of the structures for different pressure and temperature conditions, we use the approach of ab initio thermodynamics [3], which indicates that these structures should be stable under certain catalytic conditions. [1] Haruta, Catal. J. New. Mater. Electro. Sys. 7, 163 (2004). [2] R. Meyer, et al., Gold Bull. 37, 72 (2004), and references therein. [3] K. Reuter, C. Stampfl and M. Scheffler, in Handbook of Materials Modeling, Volume 1, Fundamental Models and Methods, Sidney Yip (Ed) 2005, 149-194; K. Reuter and M. Scheffler, Phys. Rev. B 65, 035406 (2002).

  20. Dynamical calculations for RHEED from a partially-ordered Cu 3Au(111) surface

    NASA Astrophysics Data System (ADS)

    Ma, Y.; Lordi, S.; Flynn, C. P.; Eades, J. A.

    1994-01-01

    A multislice formalism of Cowley and Moodie [Acta Cryst. 10 (1957) 609] with a recently developed edge patching method has been applied to the RHEED analyses on the order-disorder transition of the Cu 3Au(111) surfaces. The results give the RI- S relation as RI = 0.4 S2.224 ( RI — ratio of reflection intensities, S — long-range orde By combining the RI- T relation experimentally observable by RHEED with the simulated RI- S relation, the needed S- T relation for the transition can be resolved in a straightforward way. The results confirm what was suggested by the experiments [Mater. Res. Soc. Symp. Proc. 237 (1993) 517]: the intensities of the RHEED superstructure reflections from ordering of the Cu and Au is more than 90% sensitive to the outer monolayer alone, thus making RHEED valuable for studies of surface order. The results of the analyses on the attenuation of elastically scattered electrons inside crystal in RHEED are useful to RHEED-related surface analytical techniques: AES, REEL, EDS and RHEED-TRAXS. The investigation on the errors resulting from potential sampling has shown that choosing proper sampling rates in all three dimensions is important to the multislice simulation of RHEED.

  1. Surface-confined 2D polymerization of a brominated copper-tetraphenylporphyrin on Au(111).

    PubMed

    Smykalla, Lars; Shukrynau, Pavel; Korb, Marcus; Lang, Heinrich; Hietschold, Michael

    2015-03-01

    A coupling-limited approach for the Ullmann reaction-like on-surface synthesis of a two-dimensional covalent organic network starting from a halogenated metallo-porphyrin is demonstrated. Copper-octabromo-tetraphenylporphyrin molecules can diffuse and self-assemble when adsorbed on the inert Au(111) surface. Splitting-off of bromine atoms bonded at the macrocyclic core of the porphyrin starts at room temperature after the deposition and is monitored by X-ray photoelectron spectroscopy for different annealing steps. Direct coupling between the reactive carbon sites of the molecules is, however, hindered by the molecular shape. This leads initially to an ordered non-covalently interconnected supramolecular structure. Further heating to 300 °C and an additional hydrogen dissociation step is required to link the molecular macrocycles via a phenyl group and form large ordered polymeric networks. This approach leads to a close-packed covalently bonded network of overall good quality. The structures are characterized using scanning tunneling microscopy. Different kinds of lattice defects and, furthermore, the impact of polymerization on the HOMO-LUMO gap are discussed. Density functional theory calculations corroborate the interpretations and give further insight into the adsorption of the debrominated molecule on the surface and the geometry and coupling reaction of the polymeric structure. PMID:25672486

  2. Surface-confined 2D polymerization of a brominated copper-tetraphenylporphyrin on Au(111)

    NASA Astrophysics Data System (ADS)

    Smykalla, Lars; Shukrynau, Pavel; Korb, Marcus; Lang, Heinrich; Hietschold, Michael

    2015-02-01

    A coupling-limited approach for the Ullmann reaction-like on-surface synthesis of a two-dimensional covalent organic network starting from a halogenated metallo-porphyrin is demonstrated. Copper-octabromo-tetraphenylporphyrin molecules can diffuse and self-assemble when adsorbed on the inert Au(111) surface. Splitting-off of bromine atoms bonded at the macrocyclic core of the porphyrin starts at room temperature after the deposition and is monitored by X-ray photoelectron spectroscopy for different annealing steps. Direct coupling between the reactive carbon sites of the molecules is, however, hindered by the molecular shape. This leads initially to an ordered non-covalently interconnected supramolecular structure. Further heating to 300 °C and an additional hydrogen dissociation step is required to link the molecular macrocycles via a phenyl group and form large ordered polymeric networks. This approach leads to a close-packed covalently bonded network of overall good quality. The structures are characterized using scanning tunneling microscopy. Different kinds of lattice defects and, furthermore, the impact of polymerization on the HOMO-LUMO gap are discussed. Density functional theory calculations corroborate the interpretations and give further insight into the adsorption of the debrominated molecule on the surface and the geometry and coupling reaction of the polymeric structure.

  3. 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.

  4. 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

  5. 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

  6. 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.

  7. In situ STM study of the adsorption and electropolymerization of o-, m-, and p-ethylaniline molecules on Au(111) electrode.

    PubMed

    Chen, Sihzih; Hwuang, Chonzan; Tu, HsinLing; Wu, ChunGuey; Yau, ShuehLin; Fan, LiangJen; Yang, YawWen

    2010-08-28

    Cyclic voltammetry (CV) and in situ scanning tunneling microscopy (STM) were employed to study the adsorption and polymerization of the geometric isomers of ethylaniline (EA) on a Au(111) single-crystal electrode in 0.5 M H(2)SO(4). All three isomers, namely o-, m-, and p-EA, were adsorbed in highly ordered structures, identified as Au(111)-(4 x 2 square root(3))rect for m- and p-EA and (4 square root(3) x 4 square root(3))R30 degrees for o-EA, at the onset potentials (approximately 0.9 V [vs. reversible hydrogen electrode]) for electropolymerization. Raising the potential in excess of 0.9 V resulted in oxidation and polymerization of m- and o-EA, but decomposition of p-EA. Molecular-resolution STM imaging revealed that poly(m-EA) and poly(o-EA), denoted respectively as m- and o-PEA, exhibited distinctively different molecular shapes. More specifically, m-PEA molecules were predominantly linear and aligned preferentially in the 121 directions of the Au(111) surface; whereas o-PEA molecules were ill-defined in shape and in dimension. These differences in molecular conformation stemmed from unlike arrangements of adsorbed monomers at 0.9 V. Notably, m-EA were adsorbed in zigzags with two nearest neighbors separated by approximately 0.5 nm, which were spatially so similar to the backbones of m-PEA that m-EA molecules coupled readily when the potential was raised high enough to induce the oxidation of m-EA. In contrast, the arrangement of o-EA molecules was so different from the ideal configuration of its polymer that molecules coupled randomly to yield crooked polymer chains less than 20 nm in length. The effect of potential on the structure of m-PEA was examined also, revealing notable branching of linear m-PEA if the electrochemical potential was set at 1.1 V. PMID:20607178

  8. Fundamental studies of the chemisorption of organosulfur compounds on Au(111). Implications for molecular self-assembly on gold surfaces

    SciTech Connect

    Nuzzo, R.G.; Zegarski, B.R.; Dubois, L.H.

    1987-02-04

    Studies of the adsorption of methanethiol and dimethyl disulfide on an Au(111) surface under UHV conditions are described. Both adsorbates bind strongly, with the bonding of the disulfide being greatly favored. It is found that, under these conditions, the disulfide bond is dissociated to give a stable surface thiolate. Adsorption of methanethiol does not involve cleavage of the S-H bond. The implications of these results for solution adsorption experiments and the thermodynamics characterizing monolayer formation are discussed.

  9. Molecules with multiple switching units on a Au(111) surface: self-organization and single-molecule manipulation

    NASA Astrophysics Data System (ADS)

    Mielke, Johannes; Selvanathan, Sofia; Peters, Maike; Schwarz, Jutta; Hecht, Stefan; Grill, Leonhard

    2012-10-01

    Three different molecules, each containing two azobenzene switching units, were synthesized, successfully deposited onto a Au(111) surface by sublimation and studied by scanning tunneling microscopy at low temperatures. To investigate the influence of electronic coupling between the switching units as well as to the surface, the two azo moieties were connected either via π-conjugated para-phenylene or decoupling meta-phenylene bridges, and the number of tert-butyl groups was varied in the meta-phenylene-linked derivatives. Single molecules were found to be intact after deposition as identified by their characteristic appearance in STM images. Due to their mobility on the Au(111) surface at room temperature, the molecules spontaneously formed self-organized molecular arrangements that reflected their chemical structure. While lateral displacement of the molecules was accomplished by manipulation, trans-cis isomerization processes, typical for azobenzene switches, could not be induced.

  10. Spin-conserving and reversing photoemission from the surface states of Bi2Se3 and Au (111)

    NASA Astrophysics Data System (ADS)

    Ryoo, Ji Hoon; Park, Cheol-Hwan

    2016-02-01

    We present a theory based on first-principles calculations explaining (i) why the tunability of spin polarizations of photoelectrons from Bi2Se3 (111) depends on the band index and Bloch wave vector of the surface state and (ii) why such tunability is absent in the case of isosymmetric Au (111). The results provide not only an explanation for the recent, puzzling experimental observations but also a guide toward making highly-tunable spin-polarized electron sources from topological insulators.

  11. Approach to interfacial and intramolecular electron transfer of the diheme protein cytochrome c4 assembled on Au(111) surfaces.

    PubMed

    Chi, Qijin; Zhang, Jingdong; Arslan, Taner; Borg, Lotte; Pedersen, Gert W; Christensen, Hans E M; Nazmudtinov, Renat R; Ulstrup, Jens

    2010-04-29

    Intramolecular electron transfer (ET) between metal centers is a core feature of large protein complexes in photosynthesis, respiration, and redox enzyme catalysis. The number of microscopic redox potentials and ET rate constants is, however, prohibitive for experimental cooperative ET mapping, but two-center proteins are simple enough to offer complete communication networks. At the same time, multicenter redox proteins operate in membrane environments where conformational dynamics may lead to gated ET features different from conditions in homogeneous solution. The bacterial respiratory diheme protein Pseudomonas stutzeri cytochrome c(4) has been a target for intramolecular, interheme ET. We report here voltammetric and in situ scanning tunneling microscopy (STM) data for P. stutzeri cyt c(4) at single-crystal, atomically planar Au(111)-electrode surfaces modified by variable-length omega-mercapto-alkanoic carboxylic acids. As evidenced by in situ STM, the strongly dipolar protein is immobilized in a close to vertical orientation at this surface with the positively charged high-potential heme domain adjacent to the electrode. This orientation gives asymmetric voltammograms with two one-ET peaks in the cathodic direction and a single two-ET peak in the anodic direction. Intramolecular, interheme ET with high, 8,000-30,000 s(-1), rate constants is notably an essential part of this mechanism. The high rate constants are in striking contrast to ET reactions of P. stutzeri cyt c(4) with small reaction partners in homogeneous solution for which kinetic analysis clearly testifies to electrostatic cooperative effects but no intramolecular, interheme ET higher than 0.1-10 s(-1). This difference suggests a strong gating feature of the process. On the basis of the three-dimensional structure of P. stutzeri cyt c(4), gating is understandable due to the through-space, hydrogen-bonded electronic contact between the heme propionates which is highly sensitive to environmental

  12. In-situ X-ray diffraction and STM studies of bromide adsorption on Au(111) electrodes

    SciTech Connect

    Magnussen, O.M.; Ocko, B.M; Wang, J.X.; Adzic, R.R.

    1996-03-28

    The structure of bromide adlayers at the Au(111)-aqueous solution interface has been studied by in-situ surface X-ray scattering (SXS) and scanning tunneling microscopy (STM). Both techniques show the existence of a hexagonal close-packed adlayer phase above a critical potential and are in good quantitative agreement on the adlayer structural parameters. The bromide-bromide spacing changes continuously between 4.24 A at the critical potential and 4.03 A at a potential 300 mV more positive. The adlayer is rotated relative to the substrate by an angle dependent on potential and bromide concentration. The potential- dependent adlayer density corresponding to these structural results agrees well with Br surface excess densities from published electrochemical measurements. At very positive potentials a bromide-induced step-flow etching of the Au substrate is observed. The results are used to compare the different techniques and to discuss the adlayer structure, the phase behavior, and the halide-gold chemical interaction. 49 refs., 8 figs.

  13. 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.

  14. Direct probing of the structure and electron transfer of fullerene/ferrocene hybrid on Au(111) electrodes by in situ electrochemical STM.

    PubMed

    Chen, Ting; Wang, Dong; Gan, Li-Hua; Matsuo, Yutaka; Gu, Jing-Ying; Yan, Hui-Juan; Nakamura, Eiichi; Wan, Li-Jun

    2014-02-26

    The electron donor-acceptor dyads are an emerging class of materials showing important applications in nonlinear optics, dye-sensitized solar cells, and molecular electronics. Investigation of their structure and electron transfer at the molecular level provides insights into the structure-property relationship and can benefit the design and preparation of electron donor-acceptor dyad materials. Herein, the interface adstructure and electron transfer of buckyferrocene Fe(C60Me5)Cp, a typical electron donor-acceptor dyad, is directly probed using in situ electrochemical scanning tunneling microscopy (STM) combined with theoretical simulations. It is found that the adsorption geometry and assembled structure of Fe(C60Me5)Cp is significantly affected by the electrochemical environments. In 0.1 M HClO4 solution, Fe(C60Me5)Cp forms well-ordered monolayers and multilayers on Au(111) surfaces with molecular dimer as the building block. In 0.1 M NaClO4 solution, typical six-fold symmetric close-packed monolayer with vertically adsorbed Fe(C60Me5)Cp is formed. Upon electrochemical oxidation, the oxidized Fe(C60Me5)Cp shows higher brightness in an STM image, which facilitates the direct visualization of the interfacial electrochemical electron transfer process. Theoretical simulation indicates that the electrode potential-activated, one-electron transfer from Fe(C60Me5)Cp to the electrode leads to the change of the delocalization character of the frontier orbital in the molecule, which is responsible for the STM image contrast change. This result is beneficial for understanding the structure and property of single electron donor-acceptor dyads. It also provides a direct approach to study the electron transfer of electron donor-acceptor compounds at the molecular level. PMID:24483295

  15. 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

  16. 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.

  17. 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.

  18. 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

  19. 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

  20. STM Study of Au(111) Surface-Grafted Paramagnetic Macrocyclic Complexes [Ni2L(Hmba)](+) via Ambidentate Coligands.

    PubMed

    Salazar, Christian; Lach, Jochen; Rückerl, Florian; Baumann, Danny; Schimmel, Sebastian; Knupfer, Martin; Kersting, Berthold; Büchner, Bernd; Hess, Christian

    2016-05-10

    Molecular anchoring and electronic properties of macrocyclic complexes fixed on gold surfaces have been investigated mainly by using scanning tunnelling microscopy (STM) and complemented with X-ray photoelectron spectroscopy (XPS). Exchange-coupled macrocyclic complexes [Ni2L(Hmba)](+) were deposited via 4-mercaptobenzoate ligands on the surface of a Au(111) single crystal from a mM solution of the perchlorate salt [Ni2L(Hmba)]ClO4 in dichloromethane. The combined results from STM and XPS show the formation of large monolayers anchored via Au-S bonds with a height of about 1.5 nm. Two apparent granular structures are visible: one related to the dinickel molecular complexes (cationic structures) and a second one related to the counterions ClO4(-) which stabilize the monolayer. No type of short and long-range order is observed. STM tip-interaction with the monolayer reveals higher degradation after 8 h of measurement. Spectroscopy measurements suggest a gap of about 2.5 eV between HOMO and LUMO of the cationic structures and smaller gap in the areas related to the anionic structures. PMID:27093097

  1. Molecular layers of ZnPc and FePc on Au(111) surface: Charge transfer and chemical interaction

    NASA Astrophysics Data System (ADS)

    Ahmadi, Sareh; Shariati, M. Nina; Yu, Shun; Göthelid, Mats

    2012-08-01

    We have studied zinc phthalocyanine (ZnPc) and iron phthalocyanine (FePc) thick films and monolayers on Au(111) using photoelectron spectroscopy and x-ray absorption spectroscopy. Both molecules are adsorbed flat on the surface at monolayer. ZnPc keeps this orientation in all investigated coverages, whereas FePc molecules stand up in the thick film. The stronger inter-molecular interaction of FePc molecules leads to change of orientation, as well as higher conductivity in FePc layer in comparison with ZnPc, which is reflected in thickness-dependent differences in core-level shifts. Work function changes indicate that both molecules donate charge to Au; through the π-system. However, the Fe3d derived lowest unoccupied molecular orbital receives charge from the substrate when forming an interface state at the Fermi level. Thus, the central atom plays an important role in mediating the charge, but the charge transfer as a whole is a balance between the two different charge transfer channels; π-system and the central atom.

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

    NASA Astrophysics Data System (ADS)

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

    2009-10-01

    Electron emission spectra obtained by thermal collisions of He∗(2S1 and 2S3 ) 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 .

  3. 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.

  4. 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

  5. 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.

  6. Lifetime reduction of surface states at Cu, Ag, and Au(111) caused by impurity scattering

    NASA Astrophysics Data System (ADS)

    Heers, Swantje; Mavropoulos, Phivos; Lounis, Samir; Zeller, Rudolf; Blügel, Stefan

    2012-09-01

    We present density-functional results on the lifetime of the (111) surface state of the noble metals. We consider scattering on the Fermi surface caused by impurity atoms belonging to the 3d and 4sp series. The results are analyzed with respect to film thickness and with respect to separation of scattering into bulk or into surface states. While for impurities in the surface layer the overall trends are similar to the long-known bulk-state scattering, for adatom-induced scattering we find a surprising behavior with respect to the adatom atomic number. A plateau emerges in the scattering rate of the 3d adatoms, instead of a peak characteristic of the d resonance. Additionally, the scattering rate of 4sp adatoms changes in a zigzag pattern, contrary to a smooth parabolic increase following Linde's rule that is observed in bulk. We interpret these results in terms of the weaker charge screening and of interference effects induced by the lowering of symmetry at the surface.

  7. Constitutional Dynamics of Metal-Organic Motifs on a Au(111) Surface.

    PubMed

    Kong, Huihui; Zhang, Chi; Xie, Lei; Wang, Likun; Xu, Wei

    2016-06-13

    Constitutional dynamic chemistry (CDC), including both dynamic covalent chemistry and dynamic noncovalent chemistry, relies on reversible formation and breakage of bonds to achieve continuous changes in constitution by reorganization of components. In this regard, CDC is considered to be an efficient and appealing strategy for selective fabrication of surface nanostructures by virtue of dynamic diversity. Although constitutional dynamics of monolayered structures has been recently demonstrated at liquid/solid interfaces, most of molecular reorganization/reaction processes were thought to be irreversible under ultrahigh vacuum (UHV) conditions where CDC is therefore a challenge to be achieved. Here, we have successfully constructed a system that presents constitutional dynamics on a solid surface based on dynamic coordination chemistry, in which selective formation of metal-organic motifs is achieved under UHV conditions. The key to making this reversible switching successful is the molecule-substrate interaction as revealed by DFT calculations. PMID:27144822

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

    DOE PAGESBeta

    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

  9. Measurement of the phason dispersion of misfit dislocations on the Au(111) surface.

    PubMed

    McIntosh, E M; Kole, P R; El-Batanouny, M; Chisnall, D M; Ellis, J; Allison, W

    2013-02-22

    We report measurements of the acoustic and optical phason dispersion curves associated with the lattice of partial dislocations on the reconstructed (111) surface of gold. Our measurements of these low energy (<0.5 meV) weakly dispersive modes have been enabled by the very high resolution of the novel helium spin-echo technique. The results presented here constitute the first measurement of the phason dispersion of misfit dislocations, and possibly of excitations associated with any type of crystalline dislocations. PMID:23473169

  10. 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.

  11. Interaction of ionic liquids with noble metal surfaces: structure formation and stability of [OMIM][TFSA] and [EMIM][TFSA] on Au(111) and Ag(111).

    PubMed

    Uhl, Benedikt; Huang, Hsinhui; Alwast, Dorothea; Buchner, Florian; Behm, R Jürgen

    2015-10-01

    Aiming at a comprehensive understanding of the interaction of ionic liquids (ILs) with metal surfaces we have investigated the adsorption of two closely related ILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM][TFSA] and 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide [OMIM][TFSA], with two noble metal surfaces, Au(111) and Ag(111), under ultrahigh vacuum (UHV) conditions using scanning tunneling microscopy (STM). At room temperature, the ILs form a 2D liquid on either of the two surfaces, while at lower temperatures they condense into two-dimensional (2D) islands which exhibit ordered structures or a short-range ordered 2D glass structure. Comparison of the adlayer structures formed in the different adsorption systems and also with those determined recently for n-butyl-n-methylpyrrolidinium [TFSA](-) adlayers on Ag(111) and Au(111) (B. Uhl et al., Beilstein J. Nanotechnol., 2013, 4, 903) gains detailed insight into the adsorption geometry of the IL ions on the surface. The close similarity of the adlayer structures indicates that (i) the structure formation is dominated by the tendency to optimize the anion adsorption geometry, and that (ii) also in the present systems the cation adsorbs with the alkyl chain pointing up from the surface. PMID:26305417

  12. 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. PMID:26879625

  13. 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.

  14. 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

  15. 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

    2016-02-01

    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.

  16. 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.

  17. Growth and electronic properties of Ti nanoislands on Au(111)

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

    The initial growth of titanium nanoislands on the reconstructed Au(111) surface was investigated by Scanning Tunneling Microscopy and Scanning Tunneling Spectroscopy (STM/STS). Ti atoms evaporated onto room temperature substrate start to nucleate preferentially at the elbows of the Au(111) herringbone reconstruction; however ordered nucleation is accompanied by an early occurrence of out-of-elbow islands. Titanium islands are irregularly shaped, composed of smaller sub-units as grains of about 1-2 nm2 and their growth leads to a distortion of the underlying gold surface. We observe a retarded coalescence of titanium first layer islands with respect to other similar systems. Comparing the experimental data with a diffusive model, quantitative information about the interlayer diffusion of the first two layers is obtained. STS spectra and differential conductivity maps show peculiar electronic features outlining an important interaction between Ti atoms and the Au(111) surface.

  18. 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.

  19. 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. PMID:26429033

  20. 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.

  1. 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.

  2. Skyrmionic like spin-texture of Rashba electron scattering at magnetic adatoms deposited on the Au(111) surface

    NASA Astrophysics Data System (ADS)

    Lounis, Samir; Bringer, Andreas; Blügel, Stefan

    2010-03-01

    Surfaces are an inversion asymmetric environment. In combination with the spin-orbit interaction, surface electrons experience a Rashba effect, which leads to spin-split surface states [1]. Having an adatom on such a surface, surface states scatter at it. Interferences are created from which, surprisingly, the fingerprints of spin-orbit coupling cannot be seen with a scanning tunneling microscope (STM) [2]. Instead of a single adatom, Walls and Heller [3] proposed to use a corral of atoms to create extra spin-orbit coupling related modulations in the charge density. Resting on multiple scattering theory, we propose to visualize such effects using a spin-polarized STM considering either a single magnetic adatom or a corral of magnetic adatoms.[4pt] [1] S. Lashell, B.A. McDougall, E. Jensen, Phys. Rev. Lett.77, 3419 (1996).[0pt] [2] L. Petersen and P. Hedegård, Surf. Sci. 49, 459 (2000).[0pt] [3] J.D. Walls and E.J. Heller, Nano Letters 7, 3377 (2007).

  3. Layer by layer removal of Au atoms from passivated Au(111) surfaces using the scanning tunneling microscope: Nanoscale ``paint stripping''

    NASA Astrophysics Data System (ADS)

    Keel, J. M.; Yin, J.; Guo, Q.; Palmer, R. E.

    2002-04-01

    Layer by layer removal of gold atoms from the (111) surface of gold has been performed using the scanning tunneling microscope. The process is made possible by a chemisorbed self-assembled monolayer (SAM) of dodecanethiol molecules on the surface, which gives rise to a reduced bonding strength between the top two layers of gold atoms. The gold atoms and associated adsorbed molecules are peeled off and displaced laterally by the STM tip, and the size of the modified area (down to ˜10×10 nm) is more or less determined by the scan size.

  4. 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

  5. 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

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

    DOE PAGESBeta

    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

  7. 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.

  8. 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.

  9. Revisiting the S-Au(111) interaction: Static or Dynamic?

    SciTech Connect

    Biener, M M; Biener, J; Friend, C M

    2004-08-17

    The chemical inertness typically observed for Au does not imply a general inability to form stable bonds with non-metals but is rather a consequence of high reaction barriers. The Au-S interaction is probably the most intensively studied interaction of Au surfaces with non-metals as, for example, it plays an important role in Au ore formation, and controls the structure and dynamics of thiol-based self-assembled-monolayers (SAMs). In recent years a quite complex picture of the interaction of sulfur with Au(111) surfaces emerged, and a variety of S-induced surface structures was reported under different conditions. The majority of these structures were interpreted in terms of a static Au surface, where the positions of the Au atoms remain essentially unperturbed. Here we demonstrate that the Au(111) surface exhibits a very dynamic character upon interaction with adsorbed sulfur: low sulfur coverages modify the surface stress of the Au surface leading to lateral expansion of the surface layer; large-scale surface restructuring and incorporation of Au atoms into a growing two-dimensional AuS phase were observed with increasing sulfur coverage. These results provide new insight into the Au-S surface chemistry, and reveal the dynamic character of the Au(111) surface.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. Oxygen-Driven Porous Film Formation of Single-Crystalline Ru Deposited on Au(111).

    PubMed

    Herd, Benjamin; Langsdorf, Daniel; Sack, Christian; He, Yunbin; Over, Herbert

    2016-05-31

    We examined the interaction of oxygen with ultrathin Ru layers deposited on a Au(111) substrate using scanning tunneling microscopy, X-ray photoelectron spectroscopy, and low-energy electron diffraction. The deposition of pure Ru below one monolayer (ML) at room temperature leads to the formation of clusters on the Au(111) surface, preferentially located at the elbow sites of the herringbone reconstruction. Subsequent exposure of molecular oxygen to such a Ru-covered Au(111) surface at 680 K results in the growth of two-layer-thick Ru islands that are embedded in the top Au(111) layer. This structural reorganization of Ru is driven by the minimization of surface energy and mediated by a mobile RuOx species. Deposition of an increasing amount of Ru at 620 K (0.5-10 ML, ML = monolayer) leads to a rough Ru film on Au(111). Subsequent oxygen treatment (10(-5) mbar) at 680 K creates either a porous Ru film (<4 ML) or a flat RuO2(110) film (>6 ML) depending on the thickness of the Ru film. PMID:27173402

  15. Adsorption of oxygen on Au(111) by exposure to ozone

    NASA Astrophysics Data System (ADS)

    Saliba, N.; Parker, D. H.; Koel, B. E.

    1998-08-01

    Atomic oxygen coverages of up to 1.2 ML may be cleanly adsorbed on the Au(111) surface by exposure to O 3 at 300 K. We have studied the adsorbed oxygen layer by AES, XPS, HREELS, LEED, work function measurements and TPD. A plot of the O(519 eV)/Au(239 eV) AES ratio versus coverage is nearly linear, but a small change in slope occurs at ΘO=0.9 ML. LEED observations show no ordered superlattice for the oxygen overlayer for any coverage studied. One-dimensional ordering of the adlayer occurs at low coverages, and disordering of the substrate occurs at higher coverages. Adsorption of 1.0 ML of oxygen on Au(111) increases the work function by +0.80 eV, indicating electron transfer from the Au substrate into an oxygen adlayer. The O(1s) peak in XPS has a binding energy of 530.1 eV, showing only a small (0.3 eV) shift to a higher binding energy with increasing oxygen coverage. No shift was detected for the Au 4f 7/2 peak due to adsorption. All oxygen is removed by thermal desorption of O 2 to leave a clean Au(111) surface after heating to 600 K. TPD spectra initially show an O 2 desorption peak at 520 K at low ΘO, and the peak shifts to higher temperatures for increasing oxygen coverages up to ΘO=0.22 ML. Above this coverage, the peak shifts very slightly to higher temperatures, resulting in a peak at 550 K at ΘO=1.2 ML. Analysis of the TPD data indicates that the desorption of O 2 from Au(111) can be described by first-order kinetics with an activation energy for O 2 desorption of 30 kcal mol -1 near saturation coverage. We estimate a value for the Au-O bond dissociation energy D(Au-O) to be ˜56 kcal mol -1.

  16. 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

  17. 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

  18. Self-assembly of methanethiol on cluster arrays of Co/Au(111)

    NASA Astrophysics Data System (ADS)

    Nenchev, Georgi; Diaconescu, Bogdan; Pohl, Karsten

    2007-03-01

    Self-assembly on strained metallic interfaces is an attractive option for growing highly ordered multi-functional nanopatterns. We present a Variable Temperature STM and Auger Electron Spectroscopy study of selective adsorption of sulfur-terminated CH3SH molecules on the lattice of Co clusters on Au(111). We investigate the growth of a uniform network of Co on the reconstructed Au(111) surface, the temperature evolution of the island height and the termination, and the onset of surface alloying. Further we will show the evolution of morphology of the CH3SH film on Au (111) as a function of coverage and temperature, and the importance of the herringbone reconstruction for the SAM formation and orientation. Successful combination and control of these two processes leads to the creation of an ordered, stable patterned Co/CH3SH heterostructure with nanometer-sized unit cell.

  19. The importance of accurate adiabatic interaction potentials for the correct description of electronically nonadiabatic vibrational energy transfer: A combined experimental and theoretical study of NO(v = 3) collisions with a Au(111) surface

    SciTech Connect

    Golibrzuch, Kai; Shirhatti, Pranav R.; Kandratsenka, Alexander; Wodtke, Alec M.; Bartels, Christof; Max Planck Institute for Biophysical Chemistry, Göttingen 37077 ; Rahinov, Igor; Auerbach, Daniel J.; Max Planck Institute for Biophysical Chemistry, Göttingen 37077; Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106

    2014-01-28

    We present a combined experimental and theoretical study of NO(v = 3 → 3, 2, 1) scattering from a Au(111) surface at incidence translational energies ranging from 0.1 to 1.2 eV. Experimentally, molecular beam–surface scattering is combined with vibrational overtone pumping and quantum-state selective detection of the recoiling molecules. Theoretically, we employ a recently developed first-principles approach, which employs an Independent Electron Surface Hopping (IESH) algorithm to model the nonadiabatic dynamics on a Newns-Anderson Hamiltonian derived from density functional theory. This approach has been successful when compared to previously reported NO/Au scattering data. The experiments presented here show that vibrational relaxation probabilities increase with incidence energy of translation. The theoretical simulations incorrectly predict high relaxation probabilities at low incidence translational energy. We show that this behavior originates from trajectories exhibiting multiple bounces at the surface, associated with deeper penetration and favored (N-down) molecular orientation, resulting in a higher average number of electronic hops and thus stronger vibrational relaxation. The experimentally observed narrow angular distributions suggest that mainly single-bounce collisions are important. Restricting the simulations by selecting only single-bounce trajectories improves agreement with experiment. The multiple bounce artifacts discovered in this work are also present in simulations employing electronic friction and even for electronically adiabatic simulations, meaning they are not a direct result of the IESH algorithm. This work demonstrates how even subtle errors in the adiabatic interaction potential, especially those that influence the interaction time of the molecule with the surface, can lead to an incorrect description of electronically nonadiabatic vibrational energy transfer in molecule-surface collisions.

  20. DFT study on cysteine adsorption mechanism on Au(111) and Au(110)

    SciTech Connect

    Buimaga-Iarinca, Luiza; Floare, Calin G.; Calborean, Adrian; Turcu, Ioan

    2013-11-13

    Periodic density functional theory calculations were used to investigate relevant aspects of adsorption mechanisms of cysteine dimers in protonated form on Au(111) and Au(110) surfaces. The projected densities of states are explicitly discussed for all main chemical groups of cysteine, i.e. the amino group (NH2), the thiol group (SH) and the carboxylic group (COOH) to identify differences in adsorption mechanism. Special emphasis is put on the analysis of changes in the electronic structure of molecules adsorbed on Au(111) and Au(110) surfaces as well as the accompanying charge transfer mechanisms at molecule-substrate interaction.

  1. 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.

  2. Energetics and the magnetic state of Mn2 adsorbed on Au(111): Dimer bond distance dependence

    NASA Astrophysics Data System (ADS)

    López-Moreno, S.; Mejía-López, J.; Munoz, Francisco; Calles, A.; Morán-López, J. L.

    2016-04-01

    In this work we present a theoretical study of the adsorption Mn2 dimer on the Au(111) surface. Here we use the density functional theory to construct a map of adsorption energies, EA, of Mn2 on a Au(111) surface as a function of interatomic bond distance, dMn-Mn, among Mn atoms. We employed a 4×4 supercell of Au(111) surface which lead us to reach dMn-Mn values in the range from 2.6 to 6.8 Å. To make a full study of the adsorption energies we considered the antiferromagnetic (AFM) and ferromagnetic (FM) states of the Mn2 on the surface. The energy landscape contains local minima when the Mn atoms are adsorbed above triangular sites and barriers that the Mn adatoms have to overcome when they move across the Au(111) surface along various paths. Our results show that the lowest energy state corresponds to the state in which the Mn atoms are next-nearest neighbors and are antiferromagnetically coupled. Furthermore, all the local minima with higher bonding energy are also those in the antiferromagnetic state. Nevertheless we find a short interval in which the FM state has lower energy than the AFM one. Finally, scanning tunneling microscope simulations for various dimer configurations on surface are reported.

  3. Electron transport dynamics in redox-molecule-terminated branched oligomer wires on Au(111).

    PubMed

    Sakamoto, Ryota; Katagiri, Shunsuke; Maeda, Hiroaki; Nishimori, Yoshihiko; Miyashita, Seiji; Nishihara, Hiroshi

    2015-01-21

    Dendritic bis(terpyridine)iron(II) wires with terminal ferrocene units were synthesized on a Au(111) surface by stepwise coordination using a three-way terpyridine ligand, a ferrocene-modified terpyridine ligand, and Fe(II) ions. Potential-step chronoamperometry, which applied overpotentials to induce the redox of the terminal ferrocene, revealed an unusual electron-transport phenomenon. The current-time profile did not follow an exponential decay that is common for linear molecular wire systems. The nonexponentiality was more prominent in the forward electron-transport direction (from the terminal ferrocene to the gold electrode, oxidation) than in the reverse direction (from the gold electrode to the terminal ferrocenium, reduction). A plateau and a steep fall were observed in the former. We propose a simple electron transport mechanism based on intrawire electron hopping between two adjacent redox-active sites, and the numerical simulation thereof reproduced the series of "asymmetric" potential-step chronoamperometry results for both linear and branched bis(terpyridine)iron(II) wires. PMID:25514860

  4. The Role of d-Orbitals in the Rashba Splitting on Au(111) and Ag(111)

    NASA Astrophysics Data System (ADS)

    Lee, Hyungjun; Choi, Hyoung Joon

    2012-02-01

    We investigate the Rashba-type spin splitting in sp-derived Shockley surface states on (111) surfaces of noble metals, such as Au(111) and Ag(111), based on first-principles calculations including the spin-orbit interaction. By turning on and off l-dependent spin-orbit coupling one by one, we find that although the surface states on Au(111) have predominantly p-orbital character, the spin splitting in energy originates mainly from d-orbital character of the surface states. We also demonstrate that the spin splitting in surface states of both metallic surfaces of Au(111) and Ag(111) can be controlled by varying the sizes of d-orbital parts of the surface-state wave functions. These results show that in addition to difference in the atomic spin-orbit strength in Au and Ag, difference in d-orbital contributions to the surface states makes substantial difference in the sizes of the Rashba-type spin splitting in their surface electronic structures. This work was supported by the NRF of Korea (Grant Nos. 2009-0081204 and 2011-0018306) and KISTI Supercomputing Center (Project No. KSC-2011-C2-04).

  5. 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).

  6. 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

  7. Structure and electrocompression of electrodeposited iodine monolayers on Au(111)

    SciTech Connect

    Ocko, B.M.; Watson, G.M.; Wang, J. )

    1994-01-20

    The structure of electrodeposited iodine - from a potassium iodide (KI) electrolyte - at the Au(111) surface has been investigated using surface X-ray scattering (SXS) techniques. Two distinct incommensurate iodine monolayer phases are observed. In both of these phases the structures compress with increasing potential (electrocompression). In the lower potential phase a (px[radical]3) centered-rectangular iodine monolayer is observed in which the coverage ([theta]) increases from 36.6% to 40.9% (relative to the gold layer density) with increasing potential. At more positive potentials a rotated-hexagonal phase is formed, and [theta] increases from 41.5% to 44.5%. At the highest coverages, in both phases, the iodine-iodine nearest-neighbor spacing equals the van der Waals diameter of 4.3 [angstrom]. Analysis of the specular reflectivity gives an iodine-gold interlayer spacing of 2.35 [angstrom] and iodine coverages which are in good agreement with the in-plane diffraction results. 35 refs., 10 refs.

  8. Diffusion of the Linear CH3S-Au-SCH3 Complex on Au(111) from First Principles

    SciTech Connect

    Jiang, Deen; Dai, Sheng

    2009-01-01

    Recent experimental and computational advances have clearly established the importance of the linear alkylthiolate-Au-alkylthiolate (RS-Au-SR) complex at the interface between the thiolate groups and the gold surface. By using density functional theory-based first principles method, here we show that the elementary diffusion step of this linear complex on Au(111) has a barrier of only {approx}0.5 eV in the case of methylthiolate, indicating great mobility of the linear complex on Au(111). The role of this low barrier in the formation of a self-assembled monolayer of thiolate groups in the form of RS-Au-SR on Au(111) is discussed.

  9. 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

    2016-04-14

    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

  10. 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.

  11. 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

  12. The Structure of Dithiol Monolayers on Au(111).

    NASA Astrophysics Data System (ADS)

    Gallagher, M. C.; Macdairmid, A. R.; Banks, J. T.

    2003-03-01

    Using scanning tunneling microscopy (STM), Auger electron spectroscopy (AES), and contact angle measurements, we have studied the properties of Dithiothreitol (DTT) and Dithioerythritol (DTE) monolayers adsorbed on Au(111). DTT and DTE are both O-H functionalized α - ω dithiols. DTT is a chiral form whereas DTE is achiral. For comparison we have also studied the structure of octanethiol (n-alkanethiol, n = 8) SAMs. Octanethiol forms the characteristic close packed 3x3 monolayer with c(4x2) superstructure. In contrast, STM measurements of DTT films indicate much of the layer is disordered, however regions with local c(23x3) symmetry are observed. AES indicates the sulphur coverage for both DTT and octanethiol films are similar. AES studies involving Ellman's reagent, a marker species, also suggest a significant fraction of the DTT molecules in the adlayer bind to the gold via two Au-S bonds. Based on these results, we propose a structural model in which the majority of DTT molecules bind to the gold surface via two Au-S bonds and the distance between these two bonds is 3 times the underlying Au lattice spacing. Any differences between DTT and DTE layers due to differences in molecular structure will also be discussed.

  13. 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.

  14. Nucleation and growth of Fe and FeO nanoparticles and films on Au(111)

    SciTech Connect

    Khan, Neetha A.; Matranga, Christopher

    2008-02-01

    We have studied the formation of Fe and FeO nanoparticles and thin films on the reconstructed Au(111) surface. Scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and ion-scattering spectroscopy (ISS) were used to evaluate the structure and composition of Fe and FeO nanoparticles and films at different growth conditions. Iron grows as one monolayer high triangular particles on the Au(111) reconstruction. FeO was grown by exposing the Fe nanoparticles to molecular oxygen at 323 K, followed by annealing at 500-700 K. XPS results indicate that FeO is formed after room temperature oxidation. STM images show that well-ordered iron oxide particles form after annealing to 700 K. STM images also show evidence of a overlayer lattice with a short periodicity of 3.3 angstrom modulated by a larger periodicity of approximately 35 angstrom. The larger periodicity results from a moire pattern formed between the iron oxide overlayer and the underlying Au(111) surface.

  15. 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.

  16. 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.

  17. 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.

  18. O2 reduction by lithium on Au(111) and Pt(111)

    SciTech Connect

    Xu, Ye; Shelton Jr, William Allison

    2010-01-01

    Lithium-oxygen has one of the highest specific energies among known electrochemical couples and holds the promise of substantially boosting the energy density of portable batteries. Mechanistic knowledge of oxygen electroreduction by Li is scarce at the present time, and the factors limiting the discharge and charge efficiencies of the Li-oxygen cathode are not understood. To shed light on the fundamental surface chemistry of this oxygen reduction reaction by Li (Li-ORR), we have performed periodic density functional theory calculations in conjunction with thermodynamic modeling for two metal surfaces, Au(111) and Pt(111). The inertness of Au(111) results in a low reversible potential of 1.51 V for initial O2 reduction via superoxide (LiO2). On Pt(111), initially the dissociative adsorption of O2 is rapid and reduction involves atomic O with a reversible potential of 1.76 V, whereas the associative LiO2 channel (at 1.93 V) is expected to dominate once O2 dissociation becomes hindered by surface species. On both Au(111) and Pt(111) the lithiation of O2 significantly weakens the O-O bond, and so the selectivity of the Li-ORR products is mainly to monoxides (LixO), not peroxides (LixO2). LixO units are energetically driven to form (LixO)n aggregates, and the interfaces between (LixO)n and the metal surfaces are found also to be active sites for stabilizing LiO2 and dissociating the O-O bond. During cycling, an oxygen reduction half-cycle is expected to begin with the reduction of atomic O instead of O2 at steady state. On Au(111) this occurs at 2.27 V, whereas the greater stability of O on Pt(111) lowers the reversible potential to a maximum of 1.93 V, being limited by the delithaition of (LixO)n products to atomic O. Therefore the intrinsic reactivity of Pt(111) renders it less effective for Li-ORR than Au(111).

  19. Competition between Hexagonal and Tetragonal Hexabromobenzene Packing on Au(111).

    PubMed

    Huang, Han; Tan, Zhiyu; He, Yanwei; Liu, Jian; Sun, Jiatao; Zhao, Kang; Zhou, Zhenhong; Tian, Guo; Wong, Swee Liang; Wee, Andrew Thye Shen

    2016-03-22

    Low-temperature scanning tunneling microscope investigations reveal that hexabromobenzene (HBB) molecules arrange in either hexagonally closely packed (hcp) [Formula: see text] or tetragonal [Formula: see text] structure on Au(111) dependent on a small substrate temperature difference around 300 K. The underlying mechanism is investigated by density functional theory calculations, which reveal that substrate-mediated intermolecular noncovalent C-Br···Br-C attractions induce hcp HBB islands, keeping the well-known Au(111)-22×√3 reconstruction intact. Upon deposition at 330 K, HBB molecules trap freely diffusing Au adatoms to form tetragonal islands. This enhances the attraction between HBB and Au(111) but partially reduces the intermolecular C-Br···Br-C attractions, altering the Au(111)-22×√3 reconstruction. In both cases, the HBB molecule adsorbs on a bridge site, forming a ∼15° angle between the C-Br direction and [112̅]Au, indicating the site-specific molecule-substrate interactions. We show that the competition between intermolecular and molecule-substrate interactions determines molecule packing at the subnanometer scale, which will be helpful for crystal engineering, functional materials, and organic electronics. PMID:26905460

  20. Investigation of Metal Free Naphthalocyanine Vapor Deposited on Au(111)

    SciTech Connect

    Wiggins, Bryan C.; Hipps, Kerry W.

    2014-02-27

    Naphthalocyanines (Ncs) are promising candidates for future components in electronic devices and applications. To maximize the efficiency of Nc devices, it is critical to understand their structural and electronic properties and how these are impacted by deposition methods. The formation of a metal free naphthalocyanine (H2Nc) self-assembled monolayer on a Au(111) crystal was investigated by scanning tunneling microscopy under ultra-high-vacuum conditions at room temperature. A rigorous purification and processing procedure was developed to produce high purity, low defect, and well-ordered monolayers. High-resolution STM images reveal epitaxial growth of H2Nc on Au(111) with the observed structure having a molecular spacing of 1.6 ± 0.05 nm, with molecules orientated slightly off (roughly 2.5°) the low density packing direction of Au(111). A commensurate structure having 4 molecules per unit cell and unit cell parameters of A = 3.25 ± 0.05 nm, B = 3.17 ± 0.05 nm, and α = 87.5 ± 2° is proposed. Orbital-mediated tunneling spectroscopy was used to examine the electronic properties of individual molecules within the thin film. The first ionization potential and electron affinity of H2Nc adsorbed on Au(111) were measured to be -0.68 ± 0.03 and 1.12 ± 0.02 eV, relative to the Fermi energy.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Chiral assemblies of nickel lysinate via the corrosive adsorption of (S)-lysine on Ni/Au{111}

    NASA Astrophysics Data System (ADS)

    Wilson, K. E.; Baddeley, C. J.

    2014-11-01

    The adsorption of (S)-lysine onto submonolayer coverages of Ni on Au{111} was investigated by scanning tunnelling microscopy and reflection absorption infrared spectroscopy. Arrays of two-dimensional Ni nanoclusters were prepared on the Au{111} surface. The sticking probability of (S)-lysine was found to increase by an order of magnitude on Au surfaces templated by Ni compared to the clean Au surface. (S)-lysine corrodes Ni from the edges of clusters forming nickel lysinate complexes which self-assemble to form ordered molecular arrays. Below a threshold coverage, the Ni clusters are completely destroyed by (S)-lysine adsorption. Under these conditions, extensive restructuring of the Au steps is observed. The implications of our work for understanding the role of chiral modifiers in Ni catalysed enantioselective catalysis are discussed.

  7. 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.

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

    PubMed

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

    2013-12-01

    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. PMID:24320393

  9. Unequal-sphere packing model for simulation of the uniaxially compressed iodine adlayer on Au(111).

    PubMed

    Tkatchenko, Alexandre; Batina, Nikola

    2005-11-24

    A simple unequal-sphere packing (USP) model, based on pure geometrical principles, was applied to study the centered-rectangular iodine c(px radical3)R30 degrees adlayer on the Au(111) surface, well-known from surface X-ray structure (SXS), low energy electron diffraction (LEED), and scanning tunneling microscopy (STM) experiments. To reproduce the exact patterns observed in experiments, two selective conditions-minimum average adsorbate height and minimum adlayer roughness-were imposed. As a result, a series of adlayer patterns with c(px radical3)R30 degrees symmetry (2.3 < p < 3), with precise structural details, including atomic registry and identification of the p-bisector as the most likely trajectory for the iodine adatom movement during the so-called uniaxial compression phenomenon, were identified. In addition, using the same model, the difference between the iodine adlayer arranged in hexagonal and centered-rectangular c(px radical3)R30 degrees patterns, as in the case of Pt(111) and Au(111) surfaces, was investigated. Qualitative and quantitative comparison shows that iodine adatoms in these two arrangements differ significantly in atomic registry, distance from the substrate, and the adlayer corrugation. Our findings could be of special interest in the study of the nature of the iodine adatom bonding to different substrates (i.e., Au vs Pt). PMID:16853820

  10. 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

  11. 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.

  12. 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.

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

    DOE PAGESBeta

    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

  14. Methanethiolate Adsorption Site on Au(111): A Combined STM/DFT Study at the Single-Molecule Level

    SciTech Connect

    Maksymovych, P.; Sorescu, D.C.; Yates, J.T.

    2006-10-26

    The chemisorptive bonding of methanethiolate (CH3S) on the Au(111) surface has been investigated at a single-molecule level using low-temperature scanning tunneling microscopy (LT-STM) and density functional theory (DFT). The CH3S species were produced by STM-tip-induced dissociation of methanethiol (CH3SH) or dimethyl disulfide (CH3SSCH3) at 5 K. The adsorption site of an isolated CH3S species was assigned by comparing the experimental and calculated STM images. We conclude that the S-headgroup of chemisorbed CH3S adsorbs on the 2-fold coordinated bridge site between two Au atoms, consistent with theoretical predictions for CH3S on the nondefective Au(111) surface. Our assignment is also supported by the freezing of the tip-induced rotational dynamics of a single CH3SH molecule upon conversion to CH3S via deprotonation.

  15. 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

  16. 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.

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

    DOE PAGESBeta

    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

  18. 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.

  19. The Adsorption of C60 fullerene molecules on Nanostructured Au (111)

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Guo, Quanmin; Palmer, Richard

    2009-03-01

    The sub-monolayer growth of C60 molecules on the Au (111) surface has been studied using STM in ultra high vacuum. The C60 molecules tend to form close-packed layers due to a strong inter-molecular interaction. However, within the close-packed layer, there are finer, secondary structures that are specific to each of all the three C60/Au interfacial structures ((23x23)R30 , in-phase (R0 ) and R14 ) observed [1]. This is a consequence of the molecule-substrate interaction and our findings demonstrate a much more complex structural variation at the molecule-substrate interface than previously assumed. Furthermore, within the R14 C60 layer, slightly darker molecules (30 pm lower) aligned along the ã11-2õdirection with a ˜6 nm spacing are observed and these molecules are arranged in a reasonably well-ordered two-dimensional lattice. C60 molecules are also found to decorate the elbow sites of the herringbone reconstructed Au(111) even at room, and when fullerenes are deposited to arrays of fabricated monolayer gold stripes (gold-fingers) [2], the molecules show step-specific attachment where the step edges with the (111) micro-facet are preferentially populated.[0pt] [1] X. Zhang, F. Yin, R. E. Palmer and Q. Guo, Surf. Sci. 602 (2008) 885-892.[0pt] [2] Q. Guo, F. Yin and R. E. Palmer, Small 1 (2005) 76-79.

  20. 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.

  1. 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.

  2. Ullmann coupling reaction of aryl chlorides on Au(111) using dosed Cu as a catalyst and the programmed growth of 2D covalent organic frameworks.

    PubMed

    Shi, Ke Ji; Zhang, Xin; Shu, Chen Hui; Li, Deng Yuan; Wu, Xin Yan; Liu, Pei Nian

    2016-07-01

    The efficiency of Ullmann reaction of aryl chlorides on an Au(111) surface has been substantially increased by using dosed Cu as a catalyst. The different reactivity of aryl bromides and aryl chlorides has been exploited to design a programmed, on-surface synthesis to form 2D covalent organic frameworks. PMID:27334002

  3. Elevated-pressure chemical reactivity of carbon monoxide over Au(111)

    NASA Astrophysics Data System (ADS)

    Peters, K. F.; Steadman, P.; Isern, H.; Alvarez, J.; Ferrer, S.

    2000-11-01

    A systematic study of elevated-pressure gas-surface interactions is presented. Surface X-ray diffraction is used to study the interaction of carbon monoxide with the Au(111)-reconstructed surface. Thirteen orders of magnitude difference in pressure are probed from ultrahigh vacuum up to 2 bar of CO. Several variables are shown to influence the gas-surface interaction, including pressure, temperature, X-ray exposure and sample electric potential in the presence of X-rays. At elevated pressures of CO, the interactions range from modest rearrangement to substantial lifting of the reconstruction. There is clear evidence of a thermally activated chemical reaction involving significant displacements of gold atoms. The reactions and atomic displacements are unexpected, based on prior vacuum and theoretical studies of CO/Au, thus revealing the considerable differences associated with high gas pressures.

  4. 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. PMID:27171609

  5. Interplay between fast diffusion and molecular interaction in the formation of self-assembled nanostructures of S-cysteine on Au(111).

    PubMed

    Mateo-Martí, E; Rogero, C; Gonzalez, C; Sobrado, J M; de Andrés, P L; Martin-Gago, J A

    2010-03-16

    We have studied the first stages leading to the formation of self-assembled monolayers of S-cysteine molecules adsorbed on a Au(111) surface. Density functional theory (DFT) calculations for the adsorption of individual cysteine molecules on Au(111) at room temperature show low-energy barriers all over the 2D Au(111) unit cell. As a consequence, cysteine molecules diffuse freely on the Au(111) surface and they can be regarded as a 2D molecular gas. The balance between molecule-molecule and molecule-substrate interactions induces molecular condensation and evaporation from the morphological surface structures (steps, reconstruction edges, etc.) as revealed by scanning tunnelling microscopy (STM) images. These processes lead progressively to the formation of a number of stable arrangements, not previously reported, such as single-molecular rows, trimers, and 2D islands. The condensation of these structures is driven by the aggregation of new molecules, stabilized by the formation of electrostatic interactions between adjacent NH(3)(+) and COO(-) groups, together with adsorption at a slightly more favorable quasi-top site of the herringbone Au reconstruction. PMID:20092363

  6. Modulation of nanocavity plasmonic emission by local molecular states of C60 on Au(111).

    PubMed

    Geng, Feng; Zhang, Yang; Yu, Yunjie; Kuang, Yanmin; Liao, Yuan; Dong, Zhenchao; Hou, Jianguo

    2012-11-19

    We investigate the modulation of C60 monolayers on the nanocavity plasmonic (NCP) emission on Au(111) by tunneling electron excitation from a scanning tunneling microscope (STM) tip. STM induced luminescence spectra show not only suppressed emission, but also significant redshift of NCP emission bands on the C60 molecules relative to the bare metal surface. The redshift, together with the bias- and coverage-dependent emission feature, indicates that the C60 molecules act beyond a pure dielectric spacer, their electronic states are heavily involved in the inelastic tunneling process for plasmonic emission. A modified quantum cutoff relation is proposed to explain qualitatively the observed emission feature at both bias polarities. We also demonstrate molecularly resolved optical contrast on the C60 monolayer and discuss the contrast mechanism briefly. PMID:23187525

  7. Metal-organic extended 2D structures: Fe-PTCDA on Au(111).

    PubMed

    Alvarez, Lucía; Peláez, Samuel; Caillard, Renaud; Serena, Pedro A; Martín-Gago, José A; Méndez, Javier

    2010-07-30

    In this work we combine organic molecules of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) with iron atoms on an Au (111) substrate in ultra-high vacuum conditions at different temperatures. By means of scanning tunnelling microscopy (STM) we study the formation of stable 2D metal-organic structures. We show that at certain growth conditions (temperature, time and coverage) stable 'ladder-like' nanostructures are obtained. These are the result of connecting together two metal-organic chains through PTCDA molecules placed perpendicularly, as rungs of a ladder. These structures, stable up to 450 K, can be extended in a 2D layer covering the entire surface and presenting different rotation domains. STM images at both polarities show a contrast reversal between the two molecules at the unit cell. By means of density functional theory (DFT) calculations, we confirm the stability of these structures and that their molecular orbitals are placed separately at the different molecules. PMID:20603531

  8. Interfacial and intermolecular interactions determining the rotational orientation of C60 adsorbed on Au(111)

    NASA Astrophysics Data System (ADS)

    Paßens, Michael; Karthäuser, Silvia

    2015-12-01

    Close-packed monolayers of fullerenes on metallic substrates are very rich systems with respect to their rotational degrees of freedom and possible interactions with different adsorption sites or next neighbours. In this connection, we report in detail on the (2√3 × 2√3)R30°-superstructure of C60 with respect to the Au(111)-surface. We use molecular orbital imaging in systematic UHV-STM studies to reveal the delicate balance of interfacial and intermolecular interactions in this system. Thus, bright C60-molecules in 5:6-top and 6:6-top geometries are observed depending on the respective next neighbours. Moreover, tiny changes in the appearance of the unoccupied molecular orbitals of dim C60-molecules in hex-vac positions are identified which are caused by the respective interaction with the facets surrounding the Au-vacancy.

  9. 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.

  10. 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.

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

    DOE PAGESBeta

    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

  12. 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

  13. Emergence of chirality in hexagonally packed monolayers of hexapentyloxytriphenylene on Au(111): a joint experimental and theoretical study.

    PubMed

    Sleczkowski, Piotr; Katsonis, Nathalie; Kapitanchuk, Oleksiy; Marchenko, Alexandr; Mathevet, Fabrice; Croset, Bernard; Lacaze, Emmanuelle

    2014-11-11

    We investigate the expression of chirality in a monolayer formed spontaneously by 2,3,6,7,10,11-pentyloxytriphenylene (H5T) on Au(111). We resolve its interface morphology by combining scanning tunneling microscopy (STM) with theoretical calculations of intermolecular and interfacial interaction potentials. We observe two commensurate structures. While both of them belong to a hexagonal space group, analogical to the triangular symmetry of the molecule and the hexagonal symmetry of the substrate surface, they surprisingly reveal a 2D chiral character. The corresponding breaking of symmetry arises for two reasons. First it is due to the establishment of a large molecular density on the substrate, which leads to a rotation of the molecules with respect to the molecular network crystallographic axes to avoid steric repulsion between neighboring alkoxy chains. Second it is due to the molecule-substrate interactions, leading to commensurable large crystallographic cells associated with the large size of the molecule. As a consequence, molecular networks disoriented with respect to the high symmetry directions of the substrate are induced. The high simplicity of the intermolecular and molecule-substrate van der Waals interactions leading to these observations suggests a generic character for this kind of symmetry breaking. We demonstrate that, for similar molecular densities, only two kinds of molecular networks are stabilized by the molecule-substrate interactions. The most stable network favors the interfacial interactions between terminal alkoxy tails and Au(111). The metastable one favors a specific orientation of the triphenylene core with its symmetry axes collinear to the Au⟨110⟩. This specific orientation of the triphenylene cores with respect to Au(111) appears associated with an energy advantage larger by at least 0.26 eV with respect to the disoriented core. PMID:25317696

  14. 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

  15. Preparation and structural characterization of RuS2 nanoislands on Au(111).

    PubMed

    Cai, Tanhong; Song, Zhen; Rodriguez, Jose A; Hrbek, Jan

    2004-07-28

    Among all the transition metal sulfides, ruthenium sulfide (RuS2) has been shown to be the most active catalyst for the hydrodesulfuriztion processes. Using X-ray photoemission spectroscopy (XPS) and scanning tunneling microscopy (STM), we have found a novel approach for the preparation of RuS2 nanoislands on an Au(111) substrate. Chemical vapor deposition of Ru3(CO)12 leads to metallic Ru nanoclusters on the gold substrate. Although sulfidation has not been observed on extended Ru (0001) surface, Ru nanoclusters react with S2, forming ruthenium sulfide. While the majority of the sulfide is in the form of nanosized clusters that aggregate into clustered islands, a small fraction of the sulfide is seen as flat islands. When Ru3(CO)12 was deposited on a sulfur-modified gold substrate at elevated temperature, flat islands of ruthenium sulfide are formed exclusively. The flat islands are single-layer RuS2 nanocrystals with a (111) surface termination which exhibits an ordered array of sulfur vacancies. On such RuS2 (111) surfaces, excess sulfur is stable at low temperature and induces surface reconstruction, and desorbs at high temperature. The RuS2(111)/Au system provides an excellent model system for ruthenium sulfide catalysts. PMID:15264806

  16. Understanding domain symmetry in vanadium oxide phthalocyanine monolayers on Au (111)

    NASA Astrophysics Data System (ADS)

    Rochford, L. A.; Hancox, I.; Jones, T. S.

    2014-10-01

    Understanding the growth of organic semiconductors on solid surfaces is of key importance for the field of organic electronics. Non planar phthalocyanines have shown great promise in organic photovoltaic (OPV) applications, but little of the fundamental surface characterization to understand their structure and properties has been performed. Acquiring a deeper understanding of the molecule/substrate interaction in small molecule systems is a vital step in controlling structure/property relationships. Here we characterize the vanadium oxide phthalocyanine (VOPc)/Au (111) surface using a combination of low energy electron diffraction (LEED) and scanning tunneling microscopy (STM), obtaining complex diffraction patterns which can be understood using two dimensional fast Fourier transform (2D-FFT) analysis of STM images. These measurements reveal coexistence of three symmetrically equivalent in-plane orientations with respect to the substrate, each of which is imaged simultaneously within a single area. Combining scanning probe and diffraction measurements allows symmetrically related domains to be visualized and structurally analyzed, providing fundamental information useful for the structural engineering of non-planar phthalocyanine interfaces.

  17. 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.

  18. 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

  19. Tridentate benzylthiols on Au(111): control of self-assembly geometry.

    PubMed

    Mezour, Mohamed A; Perepichka, Iryna I; Ivasenko, Oleksandr; Lennox, R Bruce; Perepichka, Dmitrii F

    2015-03-21

    A set of hexasubstituted benzene derivatives with three thiol groups in the 1, 3, 5 positions and varied aliphatic substituents in the 2, 4, 6 positions (Me3-BTMT, Et3-BTMT, ODe3-BTMT) has been synthesized and self-assembled on Au(111). The resulting self-assembled monolayers (SAMs) are characterized by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and electrochemistry. The molecular orientation and long-range order are affected by the “gear effect” of the hexasubstituted benzene ring and van der Waals interactions between the physisorbed alkyl chains drive. Me3-BTMT adopts a standing up orientation which results in the highest molecular surface density but also the lowest degree of chemisorption (1 to 2 Au–S bonds per molecule). In contrast, Et3-BTMT favors a lying down orientation with a greater number of surface-bonded thiol groups (2 to 3) per molecule, associated with the peculiar geometry of this molecule. Finally, ODe3-BTMT adsorbs mainly in a lying down orientation, forming the SAM with the highest degree of chemisorption (all thiol groups are gold-bonded) and the lowest molecular areal density. PMID:25695677

  20. 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.

  1. Conformations of polyaniline molecules adsorbed on Au(111) probed by in situ STM and ex situ XPS and NEXAFS.

    PubMed

    Lee, YiHui; Chang, ChinZen; Yau, ShuehLin; Fan, LiangJen; Yang, YawWen; Yang, LiangYueh Ou; Itaya, Kingo

    2009-05-13

    In situ scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure (NEXAFS) have been used to examine the conformation of a monolayer of polyaniline (PAN) molecules produced on a Au(111) single-crystal electrode by anodization at 1.0 V [vs reversible hydrogen electrode (RHE)] in 0.10 M H(2)SO(4) containing 0.030 M aniline. The as-produced PAN molecules took on a well-defined linear conformation stretching for 500 A or more, as shown by in situ and ex situ STM. The XPS and NEXAFS results indicated that the linear PAN seen at 1.0 V assumed the form of an emeraldine salt made of PAN chains and (bi)sulfate anions. Shifting the potential from 1.0 to 0.7 V altered the shape of the PAN molecules from straight to crooked, which was ascribed to restructuring of the Au(111) electrified interface on the basis of voltammetric and XPS results. In situ STM showed that further decreasing the potential to 0.5 V transformed the crooked PAN threads into a mostly linear form again, with preferential alignment and formation of some locally ordered structures. PAN molecules could be reduced from emeraldine to leucoemeraldine as the potential was decreased to 0.2 V or less. In situ STM showed that the fully reduced PAN molecules were straight but mysteriously shortened to approximately 50 A in length. The conformation of PAN did not recuperate when the potential was shifted positively to 1.0 V. PMID:19361217

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

    DOE PAGESBeta

    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

  3. 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.

  4. Understanding the Kondo resonance in the d-CoPc/Au(111) adsorption system.

    PubMed

    Wang, Yu; Zheng, Xiao; Li, Bin; Yang, Jinlong

    2014-08-28

    By combining the density functional theory (DFT) and a hierarchical equations of motion (HEOM) approach, we investigate the Kondo phenomena in a composite system consisting of a dehydrogenated cobalt phthalocyanine molecule (d-CoPc) adsorbed on an Au(111) surface. DFT calculations are performed to determine the ground-state geometric and electronic structures of the adsorption system. It is found that the singly occupied dz(2) orbital of Co forms a localized spin, which could be screened by the substrate conduction electrons. This screening leads to the prominent Kondo features as observed in the scanning tunneling microscopy experiments. We then employ the HEOM approach to characterize the Kondo correlations of the adsorption system. The calculated temperature-dependent differential conductance spectra and the predicted Kondo temperature agree well with the experiments, and the universal Kondo scaling behavior is correctly reproduced. This work thus provides important insights into the relevant experiments, and it also highlights the applicability of the combined DFT+HEOM approach to the studies of strongly correlated condensed matter systems. PMID:25173036

  5. Understanding the Kondo resonance in the d-CoPc/Au(111) adsorption system

    SciTech Connect

    Wang, Yu; Zheng, Xiao Li, Bin; Yang, Jinlong

    2014-08-28

    By combining the density functional theory (DFT) and a hierarchical equations of motion (HEOM) approach, we investigate the Kondo phenomena in a composite system consisting of a dehydrogenated cobalt phthalocyanine molecule (d-CoPc) adsorbed on an Au(111) surface. DFT calculations are performed to determine the ground-state geometric and electronic structures of the adsorption system. It is found that the singly occupied d{sub z{sup 2}} orbital of Co forms a localized spin, which could be screened by the substrate conduction electrons. This screening leads to the prominent Kondo features as observed in the scanning tunneling microscopy experiments. We then employ the HEOM approach to characterize the Kondo correlations of the adsorption system. The calculated temperature-dependent differential conductance spectra and the predicted Kondo temperature agree well with the experiments, and the universal Kondo scaling behavior is correctly reproduced. This work thus provides important insights into the relevant experiments, and it also highlights the applicability of the combined DFT+HEOM approach to the studies of strongly correlated condensed matter systems.

  6. 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.

  7. Understanding the Kondo resonance in the d-CoPc/Au(111) adsorption system

    NASA Astrophysics Data System (ADS)

    Wang, Yu; Zheng, Xiao; Li, Bin; Yang, Jinlong

    2014-08-01

    By combining the density functional theory (DFT) and a hierarchical equations of motion (HEOM) approach, we investigate the Kondo phenomena in a composite system consisting of a dehydrogenated cobalt phthalocyanine molecule (d-CoPc) adsorbed on an Au(111) surface. DFT calculations are performed to determine the ground-state geometric and electronic structures of the adsorption system. It is found that the singly occupied d_{z^2} orbital of Co forms a localized spin, which could be screened by the substrate conduction electrons. This screening leads to the prominent Kondo features as observed in the scanning tunneling microscopy experiments. We then employ the HEOM approach to characterize the Kondo correlations of the adsorption system. The calculated temperature-dependent differential conductance spectra and the predicted Kondo temperature agree well with the experiments, and the universal Kondo scaling behavior is correctly reproduced. This work thus provides important insights into the relevant experiments, and it also highlights the applicability of the combined DFT+HEOM approach to the studies of strongly correlated condensed matter systems.

  8. 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

  9. Triazatriangulenium adlayers on Au(111): Superstructure as a function of alkyl side chain length

    NASA Astrophysics Data System (ADS)

    Lemke, Sonja; Ulrich, Sandra; Claußen, Frauke; Bloedorn, Andreas; Jung, Ulrich; Herges, Rainer; Magnussen, Olaf M.

    2015-02-01

    The structure of organic adlayers, formed by self-assembly of molecular platforms of triazatriangulenium ions on Au(111), was systematically studied by scanning tunneling microscopy as a function of the length of the lateral ligands for alkyl side chains from propyl to dodecyl. A series of hexagonally-ordered adlayers with spacings from 10.7 Å (propyl) to 13.6 Å (dodecyl) was found which are commensurate to the Au(111) substrate lattice, indicating localized bonding of the molecules to the metal.

  10. 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.

  11. 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

  12. 1,6-hexanedithiol monolayers on Au(111): A multitechnique structural study

    SciTech Connect

    Leung, T.Y.B.; Gerstenberg, M.C.; Lavrich, D.J.; Scoles, G.; Schreiber, F.; Poirier, G.E.

    2000-01-25

    Monolayers of 1,6-hexanedithiol [HS(CH{sub 2}){sub 6}SH] deposited on Au(111) from the gas phase were characterized by scanning tunneling microscopy (STM), grazing incidence X-ray diffraction (GIXD), and low-energy atom diffraction (LEAD). Molecular resolution STM images suggest that the molecules lie prone in a striped arrangement with an inter-row spacing of 5 {angstrom}. For the films prepared at an elevated temperature, two uniaxial incommensurate phases were found by GIXD. With respect to the surface substrate net, the diffraction patterns of both phases can be described by rectangular (p x {radical}3) nets, where p is 4.24 {+-} 0.01 and 4.30 {+-} 0.01. These values of p correspond to spacings of 12.23 {+-} 0.04 and 12.40 {+-} 0.02 {angstrom} along the nearest-neighbor (NN) direction of the substrate, whereas the spacing along the next-nearest-neighbor direction is 5 {angstrom} in both cases. The LEAD patterns can be described by a 3 x 1 superlattice with respect to the mesh observed by GIXD. Lattice nonuniformity and angular broadening along the NN direction were observed by GIXD. The structure of the striped phases is consistent with the molecules being fully extended and flat on the surface with their molecular C-C-C plane parallel to the surface. Using different growth protocols, including liquid-phase deposition, the order of the striped phases was observed to change considerably; however, no evidence of nucleation of other ordered phases was found. Even if denser phases exist, the striped phases may act as effective kinetic traps preventing the transition to other denser phases. The results of both varied growth conditions and performed annealing experiments can be explained by the strong molecule/substrate interaction in the striped phases, which is a consequence of the strong, but not site-specific, interaction of both sulfur atoms with the gold surface.

  13. 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.

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

    PubMed

    Zhang, Yi; Zhang, Yanfang; Li, Geng; Lu, Jianchen; Lin, Xiao; Tan, Yuanzhi; Feng, Xinliang; Du, Shixuan; Müllen, Klaus; Gao, Hong-Jun

    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 Cl∙∙∙Cl 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 C60 molecules on it at room temperature with low coverage. The STM images taken at low temperature show that the C60 molecules are mono-dispersed on the networks and adsorb on top of the PCHBC molecules, forming a typical concave-convex host-guest system. PMID:25770500

  15. Tridentate benzylthiols on Au(111): control of self-assembly geometry

    NASA Astrophysics Data System (ADS)

    Mezour, Mohamed A.; Perepichka, Iryna I.; Ivasenko, Oleksandr; Lennox, R. Bruce; Perepichka, Dmitrii F.

    2015-03-01

    A set of hexasubstituted benzene derivatives with three thiol groups in the 1, 3, 5 positions and varied aliphatic substituents in the 2, 4, 6 positions (Me3-BTMT, Et3-BTMT, ODe3-BTMT) has been synthesized and self-assembled on Au(111). The resulting self-assembled monolayers (SAMs) are characterized by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and electrochemistry. The molecular orientation and long-range order are affected by the ``gear effect'' of the hexasubstituted benzene ring and van der Waals interactions between the physisorbed alkyl chains drive. Me3-BTMT adopts a standing up orientation which results in the highest molecular surface density but also the lowest degree of chemisorption (1 to 2 Au-S bonds per molecule). In contrast, Et3-BTMT favors a lying down orientation with a greater number of surface-bonded thiol groups (2 to 3) per molecule, associated with the peculiar geometry of this molecule. Finally, ODe3-BTMT adsorbs mainly in a lying down orientation, forming the SAM with the highest degree of chemisorption (all thiol groups are gold-bonded) and the lowest molecular areal density.A set of hexasubstituted benzene derivatives with three thiol groups in the 1, 3, 5 positions and varied aliphatic substituents in the 2, 4, 6 positions (Me3-BTMT, Et3-BTMT, ODe3-BTMT) has been synthesized and self-assembled on Au(111). The resulting self-assembled monolayers (SAMs) are characterized by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and electrochemistry. The molecular orientation and long-range order are affected by the ``gear effect'' of the hexasubstituted benzene ring and van der Waals interactions between the physisorbed alkyl chains drive. Me3-BTMT adopts a standing up orientation which results in the highest molecular surface density but also the lowest degree of chemisorption (1 to 2 Au-S bonds per molecule). In contrast, Et3-BTMT favors a lying down orientation with a greater

  16. 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.

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

    PubMed

    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. PMID:27394092

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

    DOE PAGESBeta

    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

  20. Atomic-Scale Insight into Tautomeric Recognition, Separation, and Interconversion of Guanine Molecular Networks on Au(111).

    PubMed

    Zhang, Chi; Xie, Lei; Wang, Likun; Kong, Huihui; Tan, Qinggang; Xu, Wei

    2015-09-16

    Although tautomerization may directly affect the chemical or biological properties of molecules, real-space investigation on the tautomeric behaviors of organic molecules in a larger area of molecular networks has been scarcely reported. In this paper, we choose guanine (G) molecule as a model system. From the interplay of high-resolution scanning tunneling microscopy (STM) imaging and density functional theory (DFT) calculations, we have successfully achieved the tautomeric recognition, separation, and interconversion of G molecular networks (formed by two tautomeric forms G/9H and G/7H) with the aid of NaCl on the Au(111) surface in ultrahigh vacuum (UHV) conditions. Our results may serve as a prototypical system to provide important insights into tautomerization related issues, which should be intriguing to biochemistry, pharmaceutics, and other related fields. PMID:26322860

  1. 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).

  2. Adsorption studies of C6H6 on Cu (111), Ag (111), and Au (111) within dispersion corrected density functional theory

    NASA Astrophysics Data System (ADS)

    Chwee, T. S.; Sullivan, M. B.

    2012-10-01

    The adsorption energies and changes in surface work functions for benzene on unreconstructed Cu(111), Ag (111), and Au (111) at low coverages have been studied within the framework of dispersion corrected Kohn-Sham density functional theory. Corrections to account for long range dispersive effects between the adsorbate and metal substrate were incorporated via the exchange-hole dipole moment method of Becke and Johnson [J. Chem. Phys. 123, 154101 (2005), 10.1063/1.2065267]. We show that the dispersion corrected calculations yield significantly improved adsorption energies and work function shifts that are in good agreement with experimental values.

  3. 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.

  4. 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

  5. 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

  6. 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.

  7. 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.

  8. A novel model for the (√3 × √3)R30° alkanethiolate-Au(111) phase based on alkanethiolate-Au adatom complexes.

    PubMed

    Carro, P; Torrelles, X; Salvarezza, R C

    2014-09-21

    Self-assembled monolayers of thiols on Au(111) have attracted considerable interest from the theoretical and experimental points of view as model systems for understanding the organization of molecules on metallic surfaces, and also as key elements in nanoscience and nanotechnology. Today, there is strong theoretical and experimental evidence indicating that the surface chemistry of these monolayers at high coverage involves dithiolate-adatom (RS-Auad-SR) species, showing the existence of the (3 × 4) and c(4 × 2) lattices usually observed by scanning tunneling microscopy. However, concealing the existence of dithiolate-Au adatom species with the presence of the paradigmatic (√3 × √3)R30° lattice, which dominates the structure of long alkanethiols, still remains a challenge. Here, we propose a novel (3√3 × 3√3)R30° structural model containing RS-Auad-SR moieties based on DFT calculations which reconciles most of the experimental data observed for the (√3 × √3)R30° lattice. Our results provide a unified picture of the surface chemistry of the thiol-Au(111) system. PMID:25093279

  9. Charge transfer interactions of a Ru(II) dye complex and related ligand molecules adsorbed on Au(111)

    SciTech Connect

    Britton, Andrew J.; Weston, Matthew; O'Shea, James N.; Taylor, J. Ben; Rienzo, Anna; Mayor, Louise C.

    2011-10-28

    The interaction of the dye molecule, N3 (cis-bis(isothiocyanato)bis(2,2{sup '}-bipyridyl-4,4{sup '}-dicarboxylato) -ruthenium(II)), and related ligand molecules with a Au(111) surface has been studied using synchrotron radiation-based electron spectroscopy. Resonant photoemission spectroscopy (RPES) and autoionization of the adsorbed molecules have been used to probe the coupling between the molecules and the substrate. Evidence of charge transfer from the states near the Fermi level of the gold substrate into the lowest unoccupied molecular orbital (LUMO) of the molecules is found in the monolayer RPES spectra of both isonicotinic acid and bi-isonicotinic acid (a ligand of N3), but not for the N3 molecule itself. Calibrated x-ray absorption spectroscopy and valence band spectra of the monolayers reveals that the LUMO crosses the Fermi level of the surface in all cases, showing that charge transfer is energetically possible both from and to the molecule. A core-hole clock analysis of the resonant photoemission reveals a charge transfer time of around 4 fs from the LUMO of the N3 dye molecule to the surface. The lack of charge transfer in the opposite direction is understood in terms of the lack of spatial overlap between the {pi}*-orbitals in the aromatic rings of the bi-isonicotinic acid ligands of N3 and the gold surface.

  10. Magnetism of CoPd self-organized alloy clusters on Au(111)

    NASA Astrophysics Data System (ADS)

    Ohresser, P.; Otero, E.; Wilhelm, F.; Rogalev, A.; Goyhenex, C.; Joly, L.; Bulou, H.; Romeo, M.; Speisser, V.; Arabski, J.; Schull, G.; Scheurer, F.

    2013-12-01

    Magnetic properties of gold-encapsulated CoxPd1-x self-organized nano-clusters on Au(111) are analyzed by x-ray magnetic circular dichroism for x = 0.5, 0.7, and 1.0. The clusters are superparamagnetic with a blocking temperature decreasing with increasing Pd concentration, due to a reduction of the out-of-plane anisotropy strength. No magnetic moment is detected on Pd in these clusters, within the detection limit, contrary to thick CoPd films. Both reduction of anisotropy and vanishing Pd moment are attributed to strain.

  11. 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.

  12. Single-layer MoS2 on Au(111): Band gap renormalization and substrate interaction

    NASA Astrophysics Data System (ADS)

    Bruix, Albert; Miwa, Jill A.; Hauptmann, Nadine; Wegner, Daniel; Ulstrup, Søren; Grønborg, Signe S.; Sanders, Charlotte E.; Dendzik, Maciej; Grubišić Čabo, Antonija; Bianchi, Marco; Lauritsen, Jeppe V.; Khajetoorians, Alexander A.; Hammer, Bjørk; Hofmann, Philip

    2016-04-01

    The electronic structure of epitaxial single-layer MoS2 on Au(111) is investigated by angle-resolved photoemission spectroscopy, scanning tunneling spectroscopy, and first-principles calculations. While the band dispersion of the supported single layer is close to a free-standing layer in the vicinity of the valence-band maximum at K ¯ and the calculated electronic band gap on Au(111) is similar to that calculated for the free-standing layer, significant modifications to the band structure are observed at other points of the two-dimensional Brillouin zone: at Γ ¯, the valence-band maximum has a significantly higher binding energy than in the free MoS2 layer and the expected spin-degeneracy of the uppermost valence band at the M ¯ point cannot be observed. These band structure changes are reproduced by the calculations and can be explained by the detailed interaction of the out-of-plane MoS2 orbitals with the substrate.

  13. 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)...

  14. 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)...

  15. 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)...

  16. 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)...

  17. 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)...

  18. Two-dimensional TiO x 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 TiO x 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 Ti 2 O 3 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.

  19. Formation, characterization, and stability of methaneselenolate monolayers on Au(111): an electrochemical high-resolution photoemission spectroscopy and DFT study.

    PubMed

    Cometto, F P; Calderón, C A; Morán, M; Ruano, G; Ascolani, H; Zampieri, G; Paredes-Olivera, P; Patrito, E M

    2014-04-01

    We investigated the mechanism of formation and stability of self-assembled monolayers (SAMs) of methaneselenolate on Au(111) prepared by the immersion method in ethanolic solutions of dimethyl diselenide (DMDSe). The adsorbed species were characterized by electrochemical measurements and high-resolution photoelectron spectroscopy (HR-XPS). The importance of the headgroup on formation mechanism and the stability of the SAMs was addressed by comparatively studying methaneselenolate (MSe) and methanethiolate (MT) monolayers. Density Functional Theory (DFT) calculations were performed to identify the elementary reaction steps in the mechanisms of formation and decomposition of the monolayers. Reductive desorption and HR-XPS measurements indicated that a MSe monolayer is formed at short immersion times by the cleavage of the Se-Se bond of DMDSe. However, the monolayer decomposes at long immersion times at room temperature, as evidenced by the appearance of atomic Se on the surface. The decomposition is more pronounced for MSe than for MT monolayers. The MSe monolayer stability can be greatly improved by two modifications in the preparation method: immersion at low temperatures (-20 °C) and the addition of a reducing agent to the forming solution. PMID:24645647

  20. Advanced Materials for Neural Surface Electrodes

    PubMed Central

    Schendel, Amelia A.; Eliceiri, Kevin W.; Williams, Justin C.

    2015-01-01

    Designing electrodes for neural interfacing applications requires deep consideration of a multitude of materials factors. These factors include, but are not limited to, the stiffness, biocompatibility, biostability, dielectric, and conductivity properties of the materials involved. The combination of materials properties chosen not only determines the ability of the device to perform its intended function, but also the extent to which the body reacts to the presence of the device after implantation. Advances in the field of materials science continue to yield new and improved materials with properties well-suited for neural applications. Although many of these materials have been well-established for non-biological applications, their use in medical devices is still relatively novel. The intention of this review is to outline new material advances for neural electrode arrays, in particular those that interface with the surface of the nervous tissue, as well as to propose future directions for neural surface electrode development. PMID:26392802

  1. Surface-enhanced Raman microspectroscopy at electrode surfaces

    SciTech Connect

    Hembree D.M. Jr.; Oswald, J.C.; Smyrl, N.R.

    1987-02-01

    Surface-enhanced Raman microspectroscopy has been developed as a technique for characterizing processes occurring at the electrode/electrolyte interface. A spectroelectrochemical cell was designed to obtain Raman spectra of electrochemical species with the use of microscope optics, which allowed unambiguous placement of laser focus at the electrode surface with spatial resolution on the order of 1 ..mu..m. It was also possible to visually inspect the surface morphology of the electrode with the use of the Raman microscope in the reflected-light mode. The capabilities of the spectroelectrochemical cell were demonstrated by observation of surface-enhanced Raman scattering (SERS) for a variety of model systems (pyridine, pyridinium ion, potassium cyanide) with the use of silver, copper, and nickel electrodes. The electrochemical behavior of a commercially important gold electroplating process is also reported.

  2. A study on the formation and thermal stability of 11-MUA SAMs on Au(111)/mica and on polycrystalline gold foils.

    PubMed

    Stettner, Johanna; Frank, Paul; Griesser, Thomas; Trimmel, Gregor; Schennach, Robert; Gilli, Eduard; Winkler, Adolf

    2009-02-01

    In this article we present a comprehensive study of 11-mercaptoundecanoic acid self-assembled monolayer (SAM) formation on gold surfaces. The SAMs were prepared in ethanolic solution, utilizing two different substrates: Au(111)/mica and polycrystalline gold foils. Several experimental methods (X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and atomic force microscopy) reveal a well-defined SAM. The main focus of this work, however, was to test the stability of these SAMs by thermal desorption spectroscopy. The spectra show different desorption peaks indicating different adsorption states and/or decomposition products on the surface. The assumed monolayer peak, which can be attributed to desorption of the intact molecule, is detected at 550 K. Further desorption peaks can be found, which result, e.g., from cracking of the S-C bond on the surface, depending on the substrate quality and on the residence time under ambient conditions. PMID:19119802

  3. 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.

  4. 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

  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. 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

  7. Underpotential deposition of Cu on Au(111): Implications of the HB model

    NASA Astrophysics Data System (ADS)

    Blum, L.; Huckaby, Dale A.

    1994-05-01

    In recent papers a model for the underpotential deposition of Cu on Au(111) in the presence of bisulfate ions was proposed. In this model it was assumed that the bisulfate ions formed a square root of 3 times square root of 3 template. This template leaves a honeycomb lattice of free sites for the adsorption of copper. The clear implication is that the first peak has 2/3 of a monolayer of Cu. The second peak corresponds to the replacement of the bisulfate by copper in the adlayer. We showed also that the broad foot of the first peak is due to a second order hard hexagon like transition, which is seen experimentally by Itaya and Kolb. The interpretation, based on the STM and LEED observations, that the first peak corresponds to only 1/3 of a monolayer, is consistent with our model if it is the bisulfate ion that is actually seen in those experiments.

  8. 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

  9. Self-assembly of mechanically interlocked and threaded rings: a HREELS and XPS study of thiol-functionalised catenane and rotaxane molecules on Au(111)

    NASA Astrophysics Data System (ADS)

    De Nadaı̈, C.; Whelan, C. M.; Perollier, C.; Clarkson, G.; Leigh, D. A.; Caudano, R.; Rudolf, P.

    2000-05-01

    Thiol-functionalised catenane and rotaxane thin films were investigated in order to understand the self-assembly of such complex molecules on Au(111). Adsorption from the liquid phase at 300 K leads to the formation of overlayers without long-range order, as evidenced by high-resolution electron energy-loss spectroscopy (HREELS). As expected for thiol adsorption, the sulfur 2p binding energies determined by X-ray photoelectron spectroscopy (XPS) are consistent with the formation of thiolate surface intermediates. The properties of these films are explored as a function of annealing. Changes in vibrational spectra such as the emergence of a AuO band and variations in core-level binding energies and intensities reveal molecular rearrangement due to partial desorption. In addition, based on coherent domain sizes estimated by the angular width of the elastic beam intensity, annealing promotes long-range order within the adlayers.

  10. Squeezing and stretching Pd thin films: A high-resolution STM study of Pd/Au(111) and Pd/Cu(111) bimetallics

    NASA Astrophysics Data System (ADS)

    Blecher, Mishan E.; Lewis, Emily A.; Pronschinske, Alex; Murphy, Colin J.; Mattera, Michael F. G.; Liriano, Melissa L.; Sykes, E. Charles H.

    2016-04-01

    Pd bimetallic alloys are promising catalysts, especially for heterogeneous reactions involving hydrogen, as they exhibit increased activity and reduced demand for expensive precious metals. Using scanning tunneling microscopy, we examine the structure of Pd thin films on Cu(111) and Au(111) and demonstrate compression and expansion, respectively, of the bulk Pd lattice constant in the film. The relative binding strength of H to the two surfaces, inferred via tip-induced diffusion barriers, suggests that the strain in these systems may alter adsorbate binding and corroborates well-known trends in d-band shifts calculated by the density functional theory. Modification to the topography and activity of Pd films based on the choice of substrate metal illustrates the value of bimetallic systems for designing less expensive, tunable catalysts.

  11. Structural reconstruction and spontaneous formation of Fe polynuclears: a self-assembly of Fe-porphyrin coordination chains on Au(111) revealed by scanning tunneling microscopy.

    PubMed

    Wang, Yuxu; Zhou, Kun; Shi, Ziliang; Ma, Yu-Qiang

    2016-06-01

    A self-assembled Fe-porphyrin coordination chain structure on a Au(111) surface is investigated by scanning tunneling microscopy (STM), revealing structural reconstruction resulting from an alternative change of molecular orientations and spontaneous formation of uniformly sized Fe polynuclears. The alternation of the molecular orientations is ascribed to the cooperation of the attractive coordination and the intermolecular steric repulsion as elucidated by high-resolution STM observations. Furthermore, chemical control experiments are carried out to determine the number of atoms in an Fe polynuclear, suggesting a tentative Fe dinuclear-module that serves not only as a coordination center to link porphyrin units together but also as a "dangling" site for further functionalization by a guest terpyridine ligand. The chain structure and the Fe polynuclears are stable up to 320 K as revealed by real-time STM scanning. Annealing at higher temperatures converts the chain structure into a two-dimensional coordination structure. PMID:27167835

  12. Electronic structure and electron dynamics at an organic molecule/metal interface: interface states of tetra-tert-butyl-imine/Au(111)

    NASA Astrophysics Data System (ADS)

    Hagen, Sebastian; Luo, Ying; Haag, Rainer; Wolf, Martin; Tegeder, Petra

    2010-12-01

    Time- and angle-resolved two-photon photoemission (2PPE) spectroscopies have been used to investigated the electronic structure, electron dynamics and localization at the interface between tetra-tert-butyl imine (TBI) and Au(111). At a TBI coverage of one monolayer (ML), the two highest occupied molecular orbitals, HOMO and HOMO-1, are observed at an energy of -1.9 and -2.6 eV below the Fermi level (EF), respectively, and coincide with the d-band features of the Au substrate. In the unoccupied electronic structure, the lowest unoccupied molecular orbital (LUMO) has been observed at 1.6 eV with respect to EF. In addition, two delocalized states that arise from the modified image potential at the TBI/metal interface have been identified. Their binding energies depend strongly on the adsorption structure of the TBI adlayer, which is coverage dependent in the submonolayer (<=1 ML) regime. Thus the binding energy of the lower interface state (IS) shifts from 3.5 eV at 1.0 ML to 4.0 eV at 0.5 ML, which is accompanied by a pronounced decrease in its lifetime from 100 fs to below 10 fs. This is a result of differences in the wave function overlap with electronic states of the Au(111) substrate at different binding energies. This study shows that in order to fully understand the electronic structure of organic adsorbates at metal surfaces, not only adsorbate- and substrate-induced electronic states have to be considered but also ISs, which are the result of a potential formed by the interaction between the adsorbate and the substrate.

  13. 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.

  14. 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.}

  15. 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.

  16. Electronic structure and excited state dynamics in a dicyanovinyl-substituted oligothiophene on Au(111).

    PubMed

    Bogner, Lea; Yang, Zechao; Corso, Martina; Fitzner, Roland; Bäuerle, Peter; Franke, Katharina J; Pascual, José Ignacio; Tegeder, Petra

    2015-10-28

    Dicyanovinyl (DCV)-substituted oligothiophenes are promising donor materials in vacuum-processed small-molecule organic solar cells. Here, we studied the structural and the electronic properties of DCV-dimethyl-pentathiophene (DCV5T-Me2) adsorbed on Au(111) from submonolayer to multilayer coverages. Using a multi-technique experimental approach (low-temperature scanning tunneling microscopy/spectroscopy (STM/STS), atomic force microscopy (AFM), and two-photon photoemission (2PPE) spectroscopy), we determined the energetic position of several affinity levels as well as ionization potentials originating from the lowest unoccupied molecular orbitals (LUMO) and the highest occupied molecular orbitals (HOMO), evidencing a transport gap of 1.4 eV. Proof of an excitonic state was found to be a spectroscopic feature located at 0.6 eV below the LUMO affinity level. With increasing coverage photoemission from excitonic states gains importance. We were able to track the dynamics of several electronically excited states of multilayers by means of femtosecond time-resolved 2PPE. We resolved an intriguing relaxation dynamics involving four processes, ranging from sub-picosecond (ps) to several hundred ps time spans. These show a tendency to increase with increasing coverage. The present study provides important parameters such as energetic positions of transport levels as well as lifetimes of electronically excited states, which are essential for designing organic-molecule-based optoelectronic devices. PMID:26414934

  17. Interface Effects in Spin-crossover (SCO) Thin Films on Au(111)

    NASA Astrophysics Data System (ADS)

    Beniwal, Sumit; Zhang, Xin; Rosa, Patrick; Letard, Jean-Francois; Palamarciuc, Tatiana; Doudin, Bernard; Dowben, Peter; Enders, Axel

    2015-03-01

    Thin films of the SCO molecules [Fe(H2B(pz)2)2 (bipy)] on Au(111) are investigated. The growth mode is determined by low temperature scanning tunneling microscopy, whereas chemical and electronic properties are determined with X-ray photoemission spectroscopy (XPS) and inverse photoemission spectroscopy (IPES). The role of substrate in determining the electronic structure is determined from thickness and temperature dependent XPS. Thin films exhibit coexistence of Fe(II) and Fe(III) oxidation states, which is different from the Fe(II) oxidation state in bulk. The fraction of molecules in the Fe(II) state increases with film thickness, which suggests that the molecules at the interface are in the Fe(III) state. Cooling the films to 100 K triggers an irreversible transition from Fe(III) to Fe(II). This transition coincides with spin phase transition, where shift of the conduction band edge away from the Fermi level is observed in IPES. These results demonstrate that thin films of this complex have different phase transition behavior as compared to bulk-like samples and underline that substrate interaction is a powerful parameter to control their structural conformation, spin state as well as electronic properties.

  18. 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.

  19. 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.

  20. 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.

  1. Electron Transfer Mechanism in Gold Surface Modified with Self-Assembly Monolayers from First Principles

    NASA Astrophysics Data System (ADS)

    Lima, Filipe C. D. A.; Iost, Rodrigo M.; Crespilho, Frank N.; Caldas, Marília J.; Calzolari, Arrigo; Petrilli, Helena M.

    2013-03-01

    We report the investigation of electron tunneling mechanism of peptide ferrocenyl-glycylcystamine self-assembled monolayers (SAMs) onto Au (111) electrode surfaces. Recent experimental investigations showed that electron transfer in peptides can occur across long distances by separating the donor from the acceptor. This mechanism can be further fostered by the presence of electron donor terminations of Fc terminal units on SAMs but the charge transfer mechanism is still not clear. We study the interaction of the peptide ferrocenyl-glycylcystamine on the Au (111) from first principles calculations to evaluate the electron transfer mechanism. For this purpose, we used the Kohn Sham (KS) scheme for the Density Functional Theory (DFT) as implemented in the Quantum-ESPRESSO suit of codes, using Vandebilt ultrasoft pseudopotentials and GGA-PBE exchange correlation functional to evaluate the ground-state atomic and electronic structure of the system. The analysis of KS orbital at the Fermi Energy showed high electronic density localized in Fc molecules and the observation of a minor contribution from the solvent and counter ion. Based on the results, we infer evidences of electron tunneling mechanism from the molecule to the Au(111). We acknowledge FAPESP for grant support. Also, LCCA/USP, RICE and CENAPAD for computational resources.

  2. 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.

  3. 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.

  4. GolP-CHARMM: First-Principles Based Force Fields for the Interaction of Proteins with Au(111) and Au(100).

    PubMed

    Wright, Louise B; Rodger, P Mark; Corni, Stefano; Walsh, Tiffany R

    2013-03-12

    Computational simulation of peptide adsorption at the aqueous gold interface is key to advancing the development of many applications based on gold nanoparticles, ranging from nanomedical devices to smart biomimetic materials. Here, we present a force field, GolP-CHARMM, designed to capture peptide adsorption at both the aqueous Au(111) and Au(100) interfaces. The force field, compatible with the bio-organic force field CHARMM, is parametrized using a combination of experimental and first-principles data. Like its predecessor, GolP (Iori, F.; et al. J. Comput. Chem.2009, 30, 1465), this force field contains terms to describe the dynamic polarization of gold atoms, chemisorbing species, and the interaction between sp(2) hybridized carbon atoms and gold. A systematic study of small molecule adsorption at both surfaces using the vdW-DF functional (Dion, M.; et al. Phys. Rev. Lett.2004, 92, 246401-1. Thonhauser, T.; et al. Phys. Rev. B2007, 76, 125112) is carried out to fit and test force field parameters and also, for the first time, gives unique insights into facet selectivity of gold binding in vacuo. Energetic and spatial trends observed in our DFT calculations are reproduced by the force field under the same conditions. Finally, we use the new force field to calculate adsorption energies, under aqueous conditions, for a representative set of amino acids. These data are found to agree with experimental findings. PMID:26587623

  5. 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.

  6. Electrochemical, high-resolution photoemission spectroscopy and vdW-DFT study of the thermal stability of benzenethiol and benzeneselenol monolayers on Au(111).

    PubMed

    Cometto, F P; Patrito, E M; Paredes Olivera, P; Zampieri, G; Ascolani, H

    2012-09-25

    The preparation and thermal stability of benzenethiol and benzeneselenol self-assembled monolayers (SAMs) grown on Au(111) have been investigated by electrochemical experiments and high-resolution photoemission spectroscopy. Both techniques confirm the formation of monolayers with high packing densities (θ = 0.27-0.29 ML) and good degrees of order in both cases. Despite many similarities between the two SAMs, the thermal desorption is distinctly different: whereas the benzenethiol SAM desorbs in a single steplike process, the desorption of the benzeneselenol SAM occurs with a much lower activation energy and involves the cleavage of some Se-C bonds and a change in molecular configuration from standing up to lying down. This behavior is explained by considering the different nature of the bonding of the headgroup with the metal surface and with the phenyl ring. Density functional theory calculations show that the breakage of the Se-C bond has a lower activation energy barrier than the breakage of the S-C bond. PMID:22946792

  7. 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.

  8. Surface-enhanced Raman spectroscopy of surfactants on silver electrodes

    SciTech Connect

    Sun, Soncheng; Birke, R.L.; Lombardi, J.R. )

    1990-03-08

    Surface-enhanced Raman spectroscopy (SERS) has been used to study different kinds of surfactants (cationic, anionic, and nonionic surfactants) adsorbed on a roughened Ag electrode. Spectral assignments are made for the SERS spectrum of cetylpyridinium chloride (CPC), and it is shown that the molecule is oriented with its pyridinium ring end-on at the electrode surface at potentials positive to the point of zero charge (pzc) on Ag.

  9. Charge transfer dynamics of 3,4,9,10-perylene-tetracarboxylic-dianhydride molecules on Au(111) probed by resonant photoemission spectroscopy.

    PubMed

    Cao, Liang; Wang, Yu-Zhan; Chen, Tie-Xin; Zhang, Wen-Hua; Yu, Xiao-Jiang; Ibrahim, Kurash; Wang, Jia-Ou; Qian, Hai-Jie; Xu, Fa-Qiang; Qi, Dong-Chen; Wee, Andrew T S

    2011-11-01

    Charge transfer dynamics across the lying-down 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) organic semiconductor molecules on Au(111) interface has been investigated using the core-hole clock implementation of resonant photoemission spectroscopy. It is found that the charge transfer time scale at the PTCDA∕Au(111) interface is much larger than the C 1s core-hole lifetime of 6 fs, indicating weak electronic coupling between PTCDA and the gold substrate due to the absence of chemical reaction and∕or bonding. PMID:22070311

  10. High surface area electrode for high efficient microbial electrosynthesis

    NASA Astrophysics Data System (ADS)

    Nie, Huarong; Cui, Mengmeng; Lu, Haiyun; Zhang, Tian; Russell, Thomas; Lovley, Derek

    2012-02-01

    Microbial electrosynthesis, a process in which microorganisms directly accept electrons from an electrode to convert carbon dioxide and water into multi carbon organic compounds, affords a novel route for the generation of valuable products from electricity or even wastewater. The surface area of the electrode is critical for high production. A biocompatible, highly conductive, three-dimensional cathode was fabricated from a carbon nanotube textile composite to support the microorganism to produce acetate from carbon dioxide. The high surface area and macroscale porous structure of the intertwined CNT coated textile ?bers provides easy microbe access. The production of acetate using this cathode is 5 fold larger than that using a planar graphite electrode with the same volume. Nickel-nanowire-modified carbon electrodes, fabricated by microwave welding, increased the surface area greatly, were able to absorb more bacteria and showed a 1.5 fold increase in performance

  11. 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

  12. Self-assembled monolayers of a bis(pyrazol-1-yl)pyridine-substituted thiol on Au(111).

    PubMed

    Shen, Cai; Haryono, Marco; Grohmann, Andreas; Buck, Manfred; Weidner, Tobias; Ballav, Nirmalya; Zharnikov, Michael

    2008-11-18

    Self-assembled monolayers (SAMs) of a bis(pyrazol-1-yl)pyridine-substituted thiol (bpp-SH) on Au (111)/mica were studied with scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). Using substrates precoated with perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA), preparation at elevated temperatures yields highly ordered layers whose structure is described by a rectangular (5 x radical3) unit cell containing one molecule. The bis(pyrazol-1-yl)pyridine (bpp) units exhibit pi-stacking along the 112 direction, and they are tilted significantly. We conclude the three imine nitrogen atoms in the bpp headgroup adopt a trans,trans arrangement. PMID:18950209

  13. Covalent immobilization of native biomolecules onto Au(111) via N-hydroxysuccinimide ester functionalized self-assembled monolayers for scanning probe microscopy.

    PubMed Central

    Wagner, P; Hegner, M; Kernen, P; Zaugg, F; Semenza, G

    1996-01-01

    We have worked out a procedure for covalent binding of native biomacromolecules on flat gold surfaces for scanning probe microscopy in aqueous buffer solutions and for other nanotechnological applications, such as the direct measurement of interaction forces between immobilized macromolecules, of their elastomechanical properties, etc. It is based on the covalent immobilization of amino group-containing biomolecules (e.g., proteins, phospholipids) onto atomically flat gold surfaces via omega-functionalized self-assembled monolayers. We present the synthesis of the parent compound, dithio-bis(succinimidylundecanoate) (DSU), and a detailed study of the chemical and physical properties of the monolayer it forms spontaneously on Au(111). Scanning tunneling microscopy and atomic force microscopy (AFM) revealed a monolayer arrangement with the well-known depressions that are known to stem from an etch process during the self-assembly. The total density of the omega-N-hydroxysuccinimidyl groups on atomically flat gold was 585 pmol/cm(2), as determined by chemisorption of (14)C-labeled DSU. This corresponded to approximately 75% of the maximum density of the omega-unsubstituted alkanethiol. Measurements of the kinetics of monolayer formation showed a very fast initial phase, with total coverage within 30 S. A subsequent slower rearrangement of the chemisorbed molecules, as indicated by AFM, led to a decrease in the number of monolayer depressions in approximately 60 min. The rate of hydrolysis of the omega-N-hydroxysuccinimide groups at the monolayer/water interface was found to be very slow, even at moderately alkaline pH values. Furthermore, the binding of low-molecular-weight amines and of a model protein was investigated in detail. Images FIGURE 1 FIGURE 2 FIGURE 9 PMID:9172730

  14. 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.

  15. 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.

  16. Multilayer Interconnects for Microfabricated Surface Electrode Ion Traps

    NASA Astrophysics Data System (ADS)

    Amini, Jason; Seidelin, Signe; Wesenberg, Janus; Britton, Joe; Blakestad, Brad; Brown, Kenton; Epstein, Ryan; Home, Jonathan; Jost, John; Langer, Chris; Leibfried, Dietrich; Ozeri, Roee; Wineland, David

    2007-06-01

    Microfabricated surface electrode traps for ions are a promising technology for building scalable trapping geometries for quantum information processing. We have expanded upon our single layer gold-on-fused-silica surface electrode trap [1] to include a second patterned conducting layer under the trapping electrodes and have demonstrated the fabrication of this architecture using standard microfabrication techniques. The multilayer approach allows for a significant increase in multi-zone trapping complexity and permits improved trapping structures that are otherwise unattainable in single layer designs without vertical interconnects through the wafer. Using improved calculational methods [2], we are in the process of optimizing the planar designs to create modular elements that can be joined into larger multi-zone trapping structures. Work supported by DTO and NIST. 1. S. Seidelin et al., Phys. Rev. Lett. 96, 253003 (2006). Also, see the abstract by S. Seidelin. 2. See the abstract by J. H. Wesenberg.

  17. 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

  18. Surface-Plasmon Enhanced Transparent Electrodes in Organic Photovoltaics

    SciTech Connect

    Reilly III, T. H.; van de Lagemaat, J.; Tenent, R. C.; Morfa, A. J.; Rowlen, K. L.

    2008-01-01

    Random silver nanohole films were created through colloidal lithography techniques and metal vapor deposition. The transparent electrodes were characterized by uv-visible spectroscopy and incorporated into an organic solar cell. The test cells were evaluated for solar power-conversion efficiency and incident photon-to-current conversion efficiency. The incident photon-to-current conversion efficiency spectra displayed evidence that a nanohole film with 92 nm diameter holes induces surface-plasmon-enhanced photoconversion. The nanohole silver films demonstrate a promising route to removing the indium tin oxide transparent electrode that is ubiquitous in organic optoelectronics.

  19. Design Optimization for Anharmonic Linear Surface-Electrode Ion Trap

    NASA Astrophysics Data System (ADS)

    Liu, Wei; Chen, Shu-Ming; Chen, Ping-Xing; Wu, Wei

    2014-11-01

    An accurate and rapid method is proposed to optimize anharmonic linear surface-electrode ion trap design. Based on the method, we analyze the impact of the architectural parameters, including the width, number, and applied voltage of prerequisite active electrodes, on the number and spacing of trapped ions. Sets of optimal anharmonic trap design are given. Then the optimal designs are verified by using an ant colony optimization algorithm. The results show that the maximum ion position errors and maximum ion spacing errors are less than 1 μm up to 80. The mean of the maximum errors is nearly linear with respect to the number of trapped ions.

  20. 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.

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

    PubMed Central

    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. PMID:24994963

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

    NASA Astrophysics Data System (ADS)

    Hosseinzadeh Khaligh, Hadi; Goldthorpe, Irene A.

    2014-06-01

    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.

  3. Effects of electrode surface structure on the mechanoelectrical transduction of IPMC sensors

    NASA Astrophysics Data System (ADS)

    Palmre, Viljar; Pugal, David; Kim, Kwang

    2014-03-01

    This study investigates the effects of electrode surface structure on the mechanoelectrical transduction of IPMC sensors. A physics-based mechanoelectrical transduction model was developed that takes into account the electrode surface profile (shape) by describing the polymer-electrode interface as a Koch fractal structure. Based on the model, the electrode surface effects were experimentally investigated in case of IPMCs with Pd-Pt electrodes. IPMCs with different electrode surface structures were fabricated through electroless plating process by appropriately controlling the synthesis parameters and conditions. The changes in the electrode surface morphology and the corresponding effects on the IPMC mechanoelectrical transduction were examined. Our experimental results indicate that increasing the dispersion of Pd particles near the membrane surface, and thus the polymer-electrode interfacial area, leads to a higher peak mechanoelectrically induced voltage of IPMC. However, the overall effect of the electrode surface structure is relatively low compared to the electromechanical transduction, which is in good agreement with theoretical prediction.

  4. 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.

  5. Cryogenic ion trapping systems with surface-electrode traps

    NASA Astrophysics Data System (ADS)

    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 S88r+ 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.

  6. A van der Waals density functional investigation of carboranethiol self-assembled monolayers on Au(111).

    PubMed

    Mete, Ersen; Yılmaz, Ayşen; Danışman, Mehmet Fatih

    2016-05-14

    Isolated and full monolayer adsorption of various carboranethiol (C2B10H12S) isomers on the gold(111) surface has been investigated using both the standard and van der Waals density functional theory calculations. The effect of different molecular dipole moment orientations on the low energy adlayer geometries, the binding characteristics and the electronic properties of the self-assembled monolayers of these isomers has been studied. Specifically, the binding energy and work function changes associated with different molecules show a correlation with their dipole moments. The adsorption is favored for the isomers with dipole moments parallel to the surface. Of the two possible unit cell structures, (5 × 5) was found to be more stable than . PMID:27108565

  7. Generation of solution plasma over a large electrode surface area

    NASA Astrophysics Data System (ADS)

    Saito, Genki; Nakasugi, Yuki; Akiyama, Tomohiro

    2015-07-01

    Solution plasma has been used in a variety of fields such as nanomaterials synthesis, the degradation of harmful substances, and solution analysis. However, as existing methods are ineffective in generating plasma over a large surface area, this study investigated the contact glow discharge electrolysis, in which the plasma was generated on the electrode surface. To clarify the condition of plasma generation, the effect of electrolyte concentration and temperature on plasma formation was studied. The electrical energy needed for plasma generation is higher than that needed to sustain a plasma, and when the electrolyte temperature was increased from 32 to 90 °C at 0.01 M NaOH solution, the electric power density for vapor formation decreased from 2005 to 774 W/cm2. From these results, we determined that pre-warming of the electrolyte is quite effective in generating plasma at lower power density. In addition, lower electrolyte concentrations required higher power density for vapor formation owing to lower solution conductivity. On the basis these results, a method for large-area and flat-plate plasma generation is proposed in which an initial small area of plasma generation is extended. When used with a plate electrode, a concentration of current to the edge of the plate meant that plasma could be formed by covering the edge of the electrode plate.

  8. Effect of multipactor conditioning on technical electrode surfaces

    SciTech Connect

    Graves, T. P.; Spektor, R.; Stout, P.

    2009-11-26

    Historically, multipactor conditioning has been utilized to remove surface contaminants from rf electrodes by electron-stimulated gas desorption, and such conditioning has been shown to reduce multipactor susceptibility. Multipactor threshold improvements are due to increasing E{sub 1}, the minimum energy for the secondary electron coefficient, {delta}>1, such that resonant electrons are incapable of producing discharge-sustaining secondary emission. Using an rf amplitude sweep technique, the evolution of the multipactor threshold is measured as a function of multipactor conditioning time for a series of technical electrode surfaces. Results show over +3 dB of threshold improvement in copper and gold electrodes, while the aluminum threshold actually decreases with conditioning exposure. Additionally, these conditioning results indicate the possible voltage region for transient-mode multipaction (TMM), which can cause significant risk to rf systems such as space satellite components for which in-situ conditioning is generally not possible. Experimental results and supporting Monte Carlo particle tracking simulation results are presented.

  9. 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.

  10. Doping level influence on chemical surface of diamond electrodes

    NASA Astrophysics Data System (ADS)

    Azevedo, A. F.; Baldan, M. R.; Ferreira, N. G.

    2013-04-01

    The modification of surface bond termination promoted by the doping level on diamond electrodes is analyzed. The films were prepared by hot filament chemical vapor deposition technique using the standard mixture of H2/CH4 with an extra H2 flux passing through a bubbler containing different concentrations of B2O3 dissolved in methanol. Diamond morphology and quality were characterized by scanning electron microscopy and Raman scattering spectroscopy techniques while the changes in film surfaces were analyzed by contact angle, cyclic voltammetry and synchrotron X-ray photoelectron spectroscopy (XPS). The boron-doped diamond (BDD) films hydrophobicity, reversibility, and work potential window characteristics were related to their physical properties and chemical surface, as a function of the doping level. From the Mott-Schottky plots (MSP) and XPS analyzes, for the lightly (1018 cm-3) and highly (1020 cm-3) BDD films, the relationship between the BDD electrochemical responses and their surface bond terminations is discussed.

  11. 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.

  12. C{sub 6}H{sub 6}/Au(111): Interface dipoles, band alignment, charging energy, and van der Waals interaction

    SciTech Connect

    Abad, E.; Martinez, J. I.; Flores, F.; Ortega, J.; Dappe, Y. J.

    2011-01-28

    We analyze the benzene/Au(111) interface taking into account charging energy effects to properly describe the electronic structure of the interface and van der Waals interactions to obtain the adsorption energy and geometry. We also analyze the interface dipoles and discuss the barrier formation as a function of the metal work-function. We interpret our DFT calculations within the induced density of interface states (IDIS) model. Our results compare well with experimental and other theoretical results, showing that the dipole formation of these interfaces is due to the charge transfer between the metal and benzene, as described in the IDIS model.

  13. Photoinduced surface dynamics of CO adsorbed on a platinum electrode.

    PubMed

    Noguchi, Hidenori; Okada, Tsubasa; Uosaki, Kohei

    2006-08-10

    The surface dynamics of adsorbed CO molecules formed by dissociative adsorption of HCHO at a polycrystalline Pt electrode/electrolyte solution interface was studied by picosecond time-resolved sum-frequency generation (TR-SFG) spectroscopy. A SFG peak at 2050-2060 cm(-1) was observed at the Pt electrode in HClO(4) solution containing HCHO at 0-300 mV (vs Ag/AgCl), indicating the formation of adsorbed CO at an atop site of the Pt surface as a result of dissociative adsorption of HCHO. The peak position varied with potential by approximately 33 cm(-1)/V, as previously found in an infrared reflection absorption spectroscopy (IRAS) study. Irradiation of an intense picosecond visible pulse (25 ps, 532 nm) caused an instant intensity decrease and broadening of the CO peak accompanied by the emergence of a new broad peak at approximately 1980 cm(-1) within the time resolution of the system. These results suggest a decrease and increase in the populations of CO adsorbed on atop and bridge sites, respectively, upon visible pump pulse irradiation. PMID:16884215

  14. Laser ablation loading of a surface-electrode ion trap

    SciTech Connect

    Leibrandt, David R.; Clark, Robert J.; Labaziewicz, Jaroslaw; Antohi, Paul; Bakr, Waseem; Brown, Kenneth R.; Chuang, Isaac L.

    2007-11-15

    We demonstrate loading of {sup 88}Sr{sup +} ions by laser ablation into a mm-scale surface-electrode ion trap. The laser used for ablation is a pulsed, frequency-tripled Nd:YAG with pulse energies of 1-10 mJ and durations of 4 ns. An additional laser is not required to photoionize the ablated material. The efficiency and lifetime of several candidate materials for the laser ablation target are characterized by measuring the trapped ion fluorescence signal for a number of consecutive loads. Additionally, laser ablation is used to load traps with a trap depth (40 meV) below where electron impact ionization loading is typically successful (> or approx. 500 meV)

  15. The effects of electrode surface morphology on the actuation performance of IPMC

    NASA Astrophysics Data System (ADS)

    Palmre, Viljar; Pugal, David; Leang, Kam K.; Kim, Kwang

    2013-04-01

    It is generally understood that increasing the specific surface area of the electrodes of IPMC leads to improved electromechanical performance of the material. Most physics based models compensate the effect of high surface area of the electrodes by increasing both diffusion constant and dielectric permittivity values, while using flat electrode approximation in calculations. Herein, a model was developed to take into account the shape and area of the electrodes. High surface area of the electrodes in the model was achieved by designing 2D polymer-electrode interface as a Koch fractal structure - different generation depths and both unidirectional and random directional generations were studied. The calculations indicate that increasing the generation depth of fractals, thus surface area of the electrodes results in more overall transported charge during the actuation process. Based on the model, the effect of the specific surface area of the electrodes on the electromechanical performance was experimentally investigated. IPMCs with different Pd-Pt electrode structures were prepared and their electromechanical and electrochemical properties were examined and discussed. The methods to manipulate the surface structure of Pd-Pt electrodes were proposed.

  16. Conductive polymer foam surface improves the performance of a capacitive EEG electrode.

    PubMed

    Baek, Hyun Jae; Lee, Hong Ji; Lim, Yong Gyu; Park, Kwang Suk

    2012-12-01

    In this paper, a new conductive polymer foam-surfaced electrode was proposed for use as a capacitive EEG electrode for nonintrusive EEG measurements in out-of-hospital environments. The current capacitive electrode has a rigid surface that produces an undefined contact area due to its stiffness, which renders it unable to conform to head curvature and locally isolates hairs between the electrode surface and scalp skin, making EEG measurement through hair difficult. In order to overcome this issue, a conductive polymer foam was applied to the capacitive electrode surface to provide a cushioning effect. This enabled EEG measurement through hair without any conductive contact with bare scalp skin. Experimental results showed that the new electrode provided lower electrode-skin impedance and higher voltage gains, signal-to-noise ratios, signal-to-error ratios, and correlation coefficients between EEGs measured by capacitive and conventional resistive methods compared to a conventional capacitive electrode. In addition, the new electrode could measure EEG signals, while the conventional capacitive electrode could not. We expect that the new electrode presented here can be easily installed in a hat or helmet to create a nonintrusive wearable EEG apparatus that does not make users look strange for real-world EEG applications. PMID:22961261

  17. 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

  18. Airflow acceleration performance of asymmetric surface dielectric barrier discharge actuators at different exposed needle electrode heights

    NASA Astrophysics Data System (ADS)

    Yang, Liang; Yan, Hui-Jie; Qi, Xiao-Hua; Hua, Yue; Ren, Chun-Sheng

    2015-12-01

    The use of plasma, created by asymmetric surface dielectric barrier discharge (ASDBD), as aerodynamic actuators to control airflows, has been of widespread concern over the past decades. For the single ASDBD, the actuator performance is dependent on the geometry of actuator and the produced plasma. In this work, a new electrode configuration, i.e., a row of needle, is taken as an exposed electrode for the ASDBD plasma actuator, and the electrode height is adjustable. The effects of different electrode heights on the airflow acceleration behavior are experimentally investigated by measuring surface potential distribution, ionic wind velocity, and mean thrust force production. It is demonstrated that the airflow velocity and thrust force increase with the exposed electrode height and the best actuator performance can be obtained when the exposed electrode is adjusted to an appropriate height. The difference, as analyzed, is mainly due to the distinct plasma spatial distributions at different exposed electrode heights.

  19. 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.

  20. High surface area electrodes by template-free self-assembled hierarchical porous gold architecture.

    PubMed

    Morag, Ahiud; Golub, Tatiana; Becker, James; Jelinek, Raz

    2016-06-15

    The electrode active surface area is a crucial determinant in many electrochemical applications and devices. Porous metal substrates have been employed in electrode design, however construction of such materials generally involves multistep processes, generating in many instances electrodes exhibiting incomplete access to internal pore surfaces. Here we describe fabrication of electrodes comprising hierarchical, nano-to-microscale porous gold matrix, synthesized through spontaneous crystallization of gold thiocyanate in water. Cyclic voltammetry analysis revealed that the specific surface area of the conductive nanoporous Au microwires was very high and depended only upon the amount of gold used, not electrode areas or geometries. Application of the electrode in a pseudo-capacitor device is presented. PMID:27016632

  1. 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

  2. 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.

  3. 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.

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

    DOE PAGESBeta

    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

  5. 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. PMID:26032065

  6. Do surface electrode recordings validly represent latissimus dorsi activation patterns during shoulder tasks?

    PubMed

    Ginn, Karen A; Halaki, Mark

    2015-02-01

    Because of its superficial location surface electrodes are commonly used to record latissimus dorsi (LD) activity. Despite the fact that the recommended electrode placement is over the belly where LD is quite thin no studies have investigated the possibility of signal contamination from muscles lying deep to LD. Therefore, the aim of this study was to determine the validity of using surface electrodes to record activity from LD. Eight asymptomatic subjects performed ramped isometric (0-100% maximum load) and dynamic (70% maximum load) shoulder tasks. Intramuscular electrodes were inserted into LD and the adjacent erector spinae. Surface electrodes were placed over LD around the intramuscular electrodes. Results indicated that while there was no difference in activity level or activation pattern (ICC>0.94) recorded by the two electrode types during shoulder tasks in which LD would be expected to be active (extension and adduction), significantly lower (p<0.05) LD activity was recorded via intramuscular electrodes during the shoulder flexion and abduction tasks. Therefore, recordings of LD activity by surface electrodes overestimate LD activity during shoulder tasks when this muscle would be expected to be activated at minimum levels. Erector spinae immediately deep to LD was confirmed as a source of crosstalk contamination. PMID:25467544

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Surface defects on n-MoSe2 electrodes used in photoelectrochemical solar cells

    NASA Astrophysics Data System (ADS)

    Peraldo Bicelli, L.; Razzini, G.

    1983-12-01

    It is pointed out that stable and efficient electrochemical solar cells based on layered semiconducting materials have been obtained with single-crystal electrodes. It is necessary that the electrode materials have a very high degree of crystalline perfection, while the active surface of the electrode must be parallel to the van der Waals plane. The present investigation is concerned with two problems, taking into account the influence of local variations in the stoichiometric composition of the electrode material on the performance, and the photocatalytic process occurring on the active areas of the electrode. The obtained results provide information concerning the problems which have to be solved to obtain transition metal dichalcogenide electrodes for solid-liquid junction cells with an photoelectrochemical behavior suitable for practical applications.

  13. 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.

  14. 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

  15. 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%)

  16. 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.

  17. The effect of electrode surface roughness on the motional heating rate of electromagnetic trapped ions

    NASA Astrophysics Data System (ADS)

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

    Electric field noise is a major source of motional heating in trapped ion quantum computation. While it is well known that this noise is influenced by trap electrode geometry in patch potential and surface adsorbate models, this has only been analyzed for smooth surfaces. We investigate the dependence of electric field noise on the roughness of surface electrodes by deriving a Green's function describing this roughness, and evaluating its effects on adsorbate-surface binding energies. At cryogenic temperature, surface roughness is found to exponentially enhance or suppress heating rate, depending on the density distribution of surface adsorbates. Our result suggests that heating rates can be tuned over orders of magnitude by careful engineering of electrode surface profiles.

  18. Near-infrared surface-enhanced Raman spectroscopy. Part I: Copper and gold electrodes

    SciTech Connect

    Angel, S. M.; Katz, L. F.; Archibald, D. D.; Lin, L. T.; Honigs, D. E.

    1988-11-01

    Surface-enhanced Raman spectra of pyridine on copper and gold electrodesin the near-infrared were obtained with a Fourier transform Ramanspectrometer. Surface-enhanced Raman spectra were observed forpyridine adsorbed on copper and gold electrodes while a Nd:YAG laser(1.064 ..mu..m) was used for excitation. Good-quality spectra were recordedfor 0.08 mM pyridine on a copper electrode with a single oxidation-reductioncycle, whereas for a gold electrode, several ORCs were necessary.A very intense low-energy Raman band was observed on bothmetals at positive potentials, which may be due to a metal-oxidevibrational mode.

  19. 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. PMID:25607880

  20. High-voltage electrode optimization towards uniform surface treatment by a pulsed volume discharge

    NASA Astrophysics Data System (ADS)

    Ponomarev, A. V.; Pedos, M. S.; Scherbinin, S. V.; Mamontov, Y. I.; Ponomarev, S. V.

    2015-11-01

    In this study, the shape and material of the high-voltage electrode of an atmospheric pressure plasma generation system were optimised. The research was performed with the goal of achieving maximum uniformity of plasma treatment of the surface of the low-voltage electrode with a diameter of 100 mm. In order to generate low-temperature plasma with the volume of roughly 1 cubic decimetre, a pulsed volume discharge was used initiated with a corona discharge. The uniformity of the plasma in the region of the low-voltage electrode was assessed using a system for measuring the distribution of discharge current density. The system's low-voltage electrode - collector - was a disc of 100 mm in diameter, the conducting surface of which was divided into 64 radially located segments of equal surface area. The current at each segment was registered by a high-speed measuring system controlled by an ARM™-based 32-bit microcontroller. To facilitate the interpretation of results obtained, a computer program was developed to visualise the results. The program provides a 3D image of the current density distribution on the surface of the low-voltage electrode. Based on the results obtained an optimum shape for a high-voltage electrode was determined. Uniformity of the distribution of discharge current density in relation to distance between electrodes was studied. It was proven that the level of non-uniformity of current density distribution depends on the size of the gap between electrodes. Experiments indicated that it is advantageous to use graphite felt VGN-6 (Russian abbreviation) as the material of the high-voltage electrode's emitting surface.

  1. 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. PMID:25500614

  2. 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

  3. 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.

  4. 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

  5. Optimal surface-electrode trap lattices for quantum simulation with trapped ions.

    PubMed

    Schmied, Roman; Wesenberg, Janus H; Leibfried, Dietrich

    2009-06-12

    Trapped ions offer long internal state (spin) coherence times and strong interparticle interactions mediated by the Coulomb force. This makes them interesting candidates for quantum simulation of coupled lattices. To this end, it is desirable to be able to trap ions in arbitrary conformations with precisely controlled local potentials. We provide a general method for optimizing periodic planar radio-frequency electrodes for generating ion trapping potentials with specified trap locations and curvatures above the electrode plane. A linear-programming algorithm guarantees globally optimal electrode shapes that require only a single radio-frequency voltage source for operation. The optimization method produces final electrode shapes that are smooth and exhibit low fragmentation. Such characteristics are desirable for practical fabrication of surface-electrode trap lattices. PMID:19658931

  6. Structural evolution of trimesic acid (TMA)/Zn2 + ion network on Au(111) to final structure of (10√3 × 10√3)

    NASA Astrophysics Data System (ADS)

    Kim, Jandee; Lee, Jaesung; Rhee, Choong Kyun

    2016-02-01

    Presented is a scanning tunneling microscopy (STM) study of structural evolution of TMA/Zn2 + ion network on Au(111) to the final structure of (10√3 × 10√3) during solution phase post-modification of pristine trimesic acid (TMA) network of a (5√3 × 5√3) structure with Zn2 + ions. Coordination of Zn2 + ions into adsorbed TMA molecules transforms crown-like TMA hexamers in pristine TMA network to chevron pairs in TMA/Zn2 + ion network. Two ordered transient structures of TMA/Zn2 + ion network were observed. One is a (5√7 × 5√7) structure consisting of Zn2 + ion-containing chevron pairs and Zn2 + ion-free TMA dimers. The other is a (5√39 × 5√21) structure made of chevron pairs and chevron-pair-missing sites. An STM image showing domains of different stages of crystallization of chevron pairs demonstrates that the TMA/Zn2 + network before reaching to the final one is quite dynamic. The observed structural evolution of the TMA/Zn2 + ion network is discussed in terms of modification of configurations of adsorbed TMA as accommodating Zn2 + ions and re-ordering of Zn2 + ion-containing chevron pairs.

  7. 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.

  8. Effects of particle size and edge structure on the electronic structure, spectroscopic features, and chemical properties of Au(111)-supported MoS2 nanoparticles.

    PubMed

    Bruix, Albert; Lauritsen, Jeppe V; Hammer, Bjørk

    2016-07-01

    Materials based on MoS2 are widely used as catalysts and their structure usually consists of single-layered MoS2 nanoparticles whose edges are known to constitute the catalytically active sites. Methods based on density functional theory are used in this work to calculate the electronic structure of representative computational models of MoS2 nanoparticles supported on Au(111). By considering nanoparticles with different edge-terminations, compositions, and sizes, we describe how the electronic structure, Mo3d core-level shifts, and chemical properties (i.e. H adsorption and S vacancy formation) depend on the MoS2 nanoparticle size and structure. In addition, site-specific properties, largely inaccessible when using only slab models of MoS2 edges, are reported, which reveal that the edge sites are not uniform along the nanoparticle and largely depend on the proximity to the corners of the triangular NPs, especially when interacting with a metallic support. Furthermore, a structural motif where H atoms adsorb favourably in a bridging position between two Mo atoms is proposed as an active site for the hydrogen evolution reaction. PMID:27076269

  9. The dissipated energy of electrode surfaces: Temperature jumps from coupled transport processes

    SciTech Connect

    Bedeaux, D.; Ratkje, S.K.

    1996-03-01

    Nonequilibrium thermodynamics for surfaces has been applied to the electrode surfaces of an electrochemical cell. It is shown that the temperature of the surface differs from that of the adjacent electrolyte and electrode, and that a temperature jump exists across the surface. mathematical expressions are derived for the temperature profiles of two cells at steady-state conditions. Methods for estimating transport coefficients for the coupled transport processes at the electrode surface are discussed. Possible numerical results for the temperature profile, the overpotential, and the dissipated energy are reported. The results reflect the relative importance of heat conductivities, electric conductivities, and the Peltier coefficients for the electrode surface phenomena in combination with bulk properties. Significant temperature jumps may occur at normal electrolysis conditions 10{sup 3} to 10{sup 4} A/m, and for temperature jump coefficients which are smaller than 10{sup 3} J/s K{sup 2} m{sup 2}. The overpotential may have contributions from the Peltier coefficients for the surface larger than the ohmic contribution. The method of analysis gives new information useful for heat control of electrochemical cells, electrode kinetic studies, and interpretation of overpotentials.

  10. Direct observation of copper-induced metalation of 5,15-diphenylporphyrin on Au(111) by scanning tunneling microscopy

    NASA Astrophysics Data System (ADS)

    Xiang, Feifei; Li, Chao; Wang, Zhongping; Liu, Xiaoqing; Jiang, Danfeng; Leng, Xinli; Ling, Jie; Wang, Li

    2015-03-01

    In-situ metalation process of porphyrin molecules has been investigated by introducing guest copper atoms into porphyrins on the gold substrate in various ways. Scanning tunneling microscopy observations unambiguously demonstrate that the copper atoms aggregate to form islands directly on the gold surface at room temperature regardless of whether this gold surface is covered by the molecular layer or not. Under thermal activation of 363 K, these introduced copper atoms at the gold surface can be incorporated into the macrocycles of the molecules. Based on such experimental observations, a pathway for copper induced metalation is proposed: a copper atom prefers to enter the porphyrin macrocycles from the bottom of the molecule.

  11. On-surface synthesis of rylene-type graphene nanoribbons.

    PubMed

    Zhang, Haiming; Lin, Haiping; Sun, Kewei; Chen, Long; Zagranyarski, Yulian; Aghdassi, Nabi; Duhm, Steffen; Li, Qing; Zhong, Dingyong; Li, Youyong; Müllen, Klaus; Fuchs, Harald; Chi, Lifeng

    2015-04-01

    The narrowest armchair graphene nanoribbon (AGNR) with five carbons across the width of the GNR (5-AGNR) was synthesized on Au(111) surfaces via sequential dehalogenation processes in a mild condition by using 1,4,5,8-tetrabromonaphthalene as the molecular precursor. Gold-organic hybrids were observed by using high-resolution scanning tunneling microscopy and considered as intermediate states upon AGNR formation. Scanning tunneling spectroscopy reveals an unexpectedly large band gap of Δ = 2.8 ± 0.1 eV on Au(111) surface which can be interpreted by the hybridization of the surface states and the molecular states of the 5-AGNR. PMID:25775004

  12. A two-electrode electrochemical surface plasmon resonance sensor for investigating the electropolymerization of polyaniline

    NASA Astrophysics Data System (ADS)

    Zhang, Bing; Li, Yazhuo; Wen, Yizhang; Cai, Peijun; Wang, Xiaoping

    2015-08-01

    A novel electrochemical surface plasmon resonance (EC-SPR) sensor has been developed based on the surface plasmon resonance (SPR) combined with a two-electrode electrochemical configuration. The theory of potential-modulated for EC-SPR was described, and several factors which can induce the change of the SPR resonance angle were revealed. Comparing with the conventional three-electrode electrochemical system, the reference electrode has been eliminated in this design, and the active carbon (AC) electrode employed as the counter electrode. Due to the large specific surface area, AC presents considerable double layer capacitance at the interface of electrode and electrolyte, which can provide a constant potential during the electrochemical reactions. Using an angle modulation SPR sensor and the resolution of that is 5x10-6 RIU (refractive index units), a real-time data-smoothing algorithm is adopted to reduce the noise of the data, which can guarantee an accurate result of the resonance angle of SPR. The EC-SPR setup was used for investigating the electropolymerization of polyaniline by applying a potential of cyclic voltammetry, both of the electrochemical current and the resonance angle shift of SPR are recorded to monitor the growth process of the polymer. Comparing with the three-electrode configuration, the novel AC two-electrode system can also obtain detailed information about the polymerization process from the resonance angle shift curves, including the change of thickness and dielectric constant, deposition and transitions between different redox states of the polymer film. Experimental results demonstrated that this two-electrode EC-SPR configuration is suitable for analyzing the electropolymerization process of a conducting polymer.

  13. Effects of Electrode Surface Morphology on the Transduction of Ionic Polymer-Metal Composites

    NASA Astrophysics Data System (ADS)

    Palmre, Viljar

    Ionic polymer-metal composites (IPMCs) are innovative smart materials that exhibit electromechanical and mechanoelectrical transduction (conversion of electrical input into mechanical deformation and vice versa). Due to low driving voltage (< 5 V) and ability to operate in aqueous environment, IPMCs are attractive for developing soft actuators and sensors for underwater robots and medical devices. This dissertation focuses on investigating the effects of electrode surface morphology in the transduction of Pt and Pd-Pt electrodes-based IPMCs, with the aim to improve the electrode surface design and thereby enhance the transduction performance of the material. Firstly, the synthesis techniques are developed to control and manipulate the surface structure of the mentioned electrodes through the electroless plating process. Using these techniques, IPMCs with different electrode surface structures are fabricated. The changes in the electrode surface morphology and the resulting effects on the material's electromechanical, mechanoelectrical, electrochemical and mechanical properties area examined and analyzed. This study shows that increasing the impregnation-reduction cycles under appropriate conditions leads to the formation and growth of platinum nanoparticles with sharp tips and edges---called Pt nanothorn assemblies---at the polymer-electrode interface. IPMCs designed with such nanostructured Pt electrodes are first to be reported. The experiments demonstrate that the formation and growth of Pt nanothorn assemblies at the electrode interface increases considerably the total transported charge during the transduction, thereby increasing significantly the displacement and blocking force output of IPMC. The improvement of the mentioned electromechanical properties was 3--5 times, depending on the input voltage and frequency used. Also, the peak mechanoelectrically induced voltage increased somewhat, although the overall effect of the surface structure was relatively

  14. 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

  15. 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.

  16. GaInAsP/InP surface emitting injection laser with a ring electrode

    NASA Astrophysics Data System (ADS)

    Uchiyama, S.; Iga, K.

    1984-10-01

    A GaInAsP/InP surface emitting injection laser (lambda = 1.2 microns) with a ring electrode has been fabricated. In this structure the reflecting mirror has been separated from the p-side electrode in order to increase the reflectivity. Threshold current was 90 mA at 77 K and the operating temperature has been raised up to -85 C. The cavity length was 7.5 microns and single longitudinal mode operation was achieved.

  17. Electrochemical and surface characterization of 4-aminothiophenol adsorption at polycrystalline platinum electrodes.

    PubMed

    Rosario-Castro, Belinda I; Fachini, Estevao R; Hernández, Jessica; Pérez-Davis, Marla E; Cabrera, Carlos R

    2006-07-01

    The formation of a self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) on polycrystalline platinum electrodes has been characterized by surface analysis and electrochemistry techniques. The 4-ATP monolayer was characterized by cyclic voltammetry (CV), linear sweep voltammetry, Raman spectroscopy, reflection-absorption infrared (RAIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). CV was used to study the dependence of the adsorption time and 4-ATP solution concentration on the relative degree of coverage of 4-ATP monolayers on polycrystalline Pt electrodes. The adsorption time range probed was 24-72 h. The optimal concentration of 4-ATP needed to obtain the highest surface at the lowest adsorption time was 10 mM. RAIR and Raman spectroscopy for 4-ATP-modified platinum electrodes showed the characteristic adsorption bands for 4-ATP, such as nuNH, nuCH(arom), and nuCS(arom), indicating the adsorption on the platinum surface. The XPS spectra for the modified Pt surface presented the binding energy peaks of sulfur and nitrogen. High energy resolution XPS studies, RAIR, and Raman spectrum for platinum electrodes modified with 4-ATP indicate that the molecules are sulfur-bonded to the platinum surface. The formation of a S-Pt bond suggests that ATP adsorption leads to an amino-terminated electrode surface. The thickness of the monolayer was evaluated via angle-resolved XPS (AR-XPS) analyses, giving a value of 8 A. As evidence of the terminal amino group on the electrode surface, the chemical derivatization of the 4-ATP SAM was done with 16-Br hexadecanoic acid. This surface reaction was followed by RAIR spectroscopy. PMID:16800665

  18. 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. PMID:27372123

  19. A multipoint micro antimony pH electrode for tissue surface measurements.

    PubMed

    Lund, N; Sjöberg, F; Guldbrand, H; Walfridsson, H; Edwall, G

    1984-01-01

    Based on monocrystalline antimony we have developed a multipoint tissue surface pH electrode. The six electrodes were produced by spark cutting from a large antimony single crystal. The electrodes were then cast in epoxy resin in a ring shaped structure which fitted around the MDO oxygen electrode. The antimony electrode was ground and polished to expose an undisturbed closely packed crystal plane of antimony to the measuring solution. Before and after monitoring periods standardization was performed in TRIS buffers of pH 6.72, 7.32 and 7.74 at 37 degrees C. Antimony electrode potential is influenced by oxygen. Therefore, mean tissue oxygen pressure was registered simultaneously with an MDO electrode. The oxygen sensitivity factor used in this study was 18mV/logpO2. The correction factor for the antimony electrode oxygen dependence, measured in vitro, seemed to be correct also for the in vivo state. This, however, needs further investigation. To illustrate the usefulness of the multipoint pH electrode seven normal state rabbits were studied, and thereafter four - one each in a hypoxic, hypocarbic, hypovolemic or hyperoxic situation. In the normal state tissue pH measured on a skeletal muscle surface varied from 7.0 to 7.4. In the case of tissue microcirculation shutdown (in the hypocarbic or the hypovolemic situations), the initial reaction was a scattering of the pH values, and then the development of tissue acidosis. Our conclusion is that the use of a multipoint pH sensor enables improved and more detailed monitoring of the tissue acid-base status. PMID:6546135

  20. A pH-Sensitive Supramolecular Switch Based on Mixed Carboxylic Acid Terminated Self-Assembled Monolayers on Au(111).

    PubMed

    Jacquelín, Daniela K; Pérez, Manuel A; Euti, Esteban M; Arisnabarreta, Nicolás; Cometto, Fernando P; Paredes-Olivera, Patricia; Patrito, E Martín

    2016-02-01

    We show that homogeneously mixed self-assembled monolayers (SAMs) of mercaptoalkanoic acids of different chain lengths can be used to build up a pH-sensitive supramolecular switch. The acids with short and long alkyl chains interact via the strong hydrogen bond between carboxylic acid groups. The pH acts as a trigger by breaking or restoring the hydrogen bond interaction in basic or acidic solutions, respectively. The corresponding changes in the monolayer structure were determined by ellipsometry, surface-enhanced Raman spectroscopy, and contact angle measurements. Density functional theory (DFT) calculations were performed to elucidate the structures of interacting molecules compatible with the surface coverage obtained from electrochemical reductive desorption experiments. The simplicity of the preparation procedure assures a high reproducibility whereas the stability of the homogeneous mixed SAM guarantees the reversibility of the switching process. PMID:26799556

  1. TWT efficiency enhancement with textured carbon surfaces on copper MDC electrodes. [multistage depressed collectors

    NASA Technical Reports Server (NTRS)

    Curren, A. N.; Ramins, P.

    1985-01-01

    A method of improving the efficiency of multistage depressed collectors (MDC's) for traveling-wave tubes (TWT's) has been demonstrated at the NASA Lewis Research Center. A significant increase in MDC efficiency was brought about by the application of a thin layer of highly-textured carbon to the surfaces of oxygen-free, high-conductivity (OFHC) copper collector electrodes in an experimental TWT. The textured carbon layer was applied by means of a NASA developed sputtering procedure. In an experimental investigation recently completed, this electrode surface modification resulted in an increase in MDC efficiency by as much as 8.6 percentage points relative to that of the same MDC with untreated copper electrode surfaces. This increase in MDC efficiency was reflected by an increase in overall TWT efficiency by as much as 5.4 percentage points.

  2. 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.

  3. TWT efficiency enhancement with textured carbon surfaces on copper MDC electrodes

    NASA Astrophysics Data System (ADS)

    Curren, A. N.; Ramins, P.

    1985-12-01

    A method of improving the efficiency of multistage depressed collectors (MDC's) for traveling-wave tubes (TWT's) has been demonstrated at the NASA Lewis Research Center. A significant increase in MDC efficiency was brought about by the application of a thin layer of highly-textured carbon to the surfaces of oxygen-free, high-conductivity (OFHC) copper collector electrodes in an experimental TWT. The textured carbon layer was applied by means of a NASA developed sputtering procedure. In an experimental investigation recently completed, this electrode surface modification resulted in an increase in MDC efficiency by as much as 8.6 percentage points relative to that of the same MDC with untreated copper electrode surfaces. This increase in MDC efficiency was reflected by an increase in overall TWT efficiency by as much as 5.4 percentage points.

  4. 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.

  5. Long electrodes for radio frequency ablation: comparative study of surface versus intramural application.

    PubMed

    Berjano, Enrique J; Hornero, Fernando; Atienza, Felipe; Montero, Anastasio

    2003-12-01

    There is increasing use of radio frequency (RF) ablation with long electrodes in the intraoperative treatment of atrial fibrillation. Nevertheless, the disparity in the lesion geometry in both depth and width is the major pitfall in the use of RF currents. The objective of this study was to differentiate the shape and size of long lesions created by three surface application electrodes (SAE) and two intramural electrodes (IE). The SAE included a standard multi-polar catheter, and two standard electrosurgical pencils. The IE consisted of a needle and a wire both intramurally buried. The lesions were created on fresh fragments of porcine ventricular tissue. The IE created lesions with a curved prism-like shape around the electrode body, with homogeneous characteristics along the lesion trajectory. On the contrary, the lesions created with the SAE were in the shape of an hourglass. They showed a different geometry between the central zone and the edge zone (p<0.001 for depth and surface width). Electrical impedance evolution was recorded during the RF heating. We observed a slow decrease of the impedance in all the electrodes, except in the wire electrode. In conclusion, the results suggest that the IE might be a more suitable option than SAE when it is necessary to create long and homogeneous thermal lesions. PMID:14630474

  6. Highly Efficient Electrohydrodynamic Pumping: Molecular Isomer Effect of Dielectric Liquids, and Surface States of Electrodes.

    PubMed

    Abe, Hiroshi; Imai, Yusuke; Tokunaga, Naoki; Yamashita, Yasuhiro; Sasaki, Yoshiki

    2015-11-11

    Highly efficient electrohydrodynamic (EHD) pumping was obtained by a combination of a dielectric liquid having a molecular isomer and electrodes with a smooth surface. Four kinds of surface states of Cu electrodes were processed by conventional mechanical polishing, fine diamond paste polishing, chemical etching and Au vapor deposition. A series of hydrofluoroether liquids (HFEs) were used as dielectric liquids: C3F7OCH3 (HFE-7000), C4F9OCH3 (HFE-7100), C4F9OC2H5 (HFE-7200), C6F13OCH3 (HFE-7300), and C5H5F6OC3HF6 (HFE-7600). The coexistence of normal (n-) and isomer (i-) HFEs and their molar fractions were examined by NMR spectroscopy. Among the dielectric liquids, the hybrid n- and i-HFE-7600 showed highly efficient EHD pumping, where the electric current, I, was sufficiently suppressed by the smooth surface of the electrodes. The maximum hydrostatic pressure Δpmax was ∼7500 Pa with 12 kV and I = 19 μA. The smooth surface of the electrodes contributes not only to the formation of a stable electric double layer (EDL) but also to the prevention of charge injection from the electrodes. Polarization pumping derived from the stable EDL enables highly efficient energy transfer without discharging, or damage to the sample and electrodes. The dipole moments of the HFEs were estimated by density functional theory calculations. The hydrostatic pressure was found to be proportional to the difference in the calculated dipole moment between n- and i-HFEs. Numerical simulations were carried out to examine the experimentally obtained electrode gap dependence of the hydrostatic pressure. PMID:26465161

  7. Current distribution over the electrode surface in a cylindrical VRLA cell during discharge

    NASA Astrophysics Data System (ADS)

    Křivák, Petr; Bača, Petr; Calábek, Milan; Micka, Karel; Král, Petr

    The current distribution over the surface of cylindrical VRLA accumulator electrodes for hybrid electric vehicles during discharge was determined mathematically by using an equivalent electrical circuit. The dependence of the internal resistance on the current and on the charge passed was determined by measurements on an experimental cell. The results are presented in the form of 3D diagrams for different states of discharge. The effect of the configuration of the current tabs on the current distribution over the electrode surface during discharge is discussed.

  8. 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

  9. Modification of the surface morphology of the silicon substrate for boron-doped diamond electrodes in electrochemical wastewater treatment applications

    NASA Astrophysics Data System (ADS)

    Bak, Ji-Yoon; Lee, Choong-Hyun; Kim, Jung-Do; Lim, Dae-Soon

    2016-01-01

    For electrochemical wastewater treatment applications, textured boron-doped diamond (BDD) electrodes were fabricated by using a simple and cost-effective etching process. On the basis of the surface area measurement, the etching time was optimized in order to achieve higher electrochemical wastewater treatment performance. The surface structure, electrochemical properties, and electrochemical oxidation performance of the electrodes were characterized by using Raman spectroscopy and atomic force microscopy, in addition to electrochemical techniques. The textured BDD electrode demonstrated a dense and large surface area with no change in the film's properties. The effective surface area of the textured BDD electrode was approximately twice as large as that of the planar BDD electrode. The electrochemical results clearly demonstrate that the enhanced surface area of the BDD electrode achieves a higher current efficiency and much lower energy consumption in the electrochemical oxidation of methyl-orange.

  10. A MEMS fabricated flexible electrode array for recording surface field potentials.

    PubMed

    Hollenberg, Brian A; Richards, Cecilia D; Richards, Robert; Bahr, David F; Rector, David M

    2006-05-15

    We developed a method to microfabricate flexible electrode arrays on a thin Kapton substrate, which was engineered to minimize trauma when inserted between the dura and skull to obtain surface EEG recordings. The array consisted of 64 gold electrodes, each 150microm in diameter on a 750microm spaced 8x8 grid. Using photolithographic procedures, any arrangement of electrodes can be implemented. We used the electrode array to record evoked response signals to create topographical maps of the whisker barrels on the cortical surface with excellent signal stability over a period of 8h. The materials used for this fabrication are potentially biologically inert and, with some additional modifications to the design, can be chronically implanted with minimal side effects. Retinal prosthesis, human neurosurgery, and neurological research are all limited to some degree by the resolution and biological compatibility of the implants used. This type of array could greatly enhance the spatial resolution, signal quality, and stability of implantable surface electrode arrays. PMID:16352343

  11. Surface-initiated growth of ionomer films from pt-modified gold electrodes.

    PubMed

    Berron, Brad J; Faulkner, Christopher J; Fischer, Remington E; Payne, P Andrew; Jennings, G Kane

    2009-11-01

    The ability to chemically wire ionomer films to electrode surfaces can promote transport near interfaces and impact a host of energy-related applications. Here, we demonstrate proof-of-concept principles for the surface-initiated ring-opening metathesis polymerization (SI-ROMP) of norbornene (NB), 5-butylnorbornene (NBH4), and 5-perfluorobutylnorbornene (NBF4) from Pt-modified gold substrates and the subsequent sulfonation of olefins along the polymer backbones to produce ultrathin sulfonated polymer films. Prior to sulfonation, the films are hydrophobic and exhibit large barriers against ion transport, but sulfonation dramatically reduces the resistance of the films by providing pathways for proton diffusion. Sulfonated films derived from NBF4 and NBH4 yield more anodic potentials for oxygen reduction than those derived from NB or unfunctionalized electrodes. These improvements are consistent with hydrophobic structuring by the fluorocarbon or hydrocarbon side groups to minimize interfacial flooding and generate pathways for enhanced O(2) permeation near the interface. Importantly, we demonstrate that the sulfonated polymer chains remain anchored to the surface during voltammetry for oxygen reduction whereas short-chain thiolates that do not tether polymer are removed from the substrate. This approach, which we extend to unmodified gold electrodes at neutral pH, presents a method of cleaning the ionomer/electrode interface to remove molecular components that may hamper the performance of the electrode. PMID:19637878

  12. 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

  13. 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

  14. 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

  15. Estimation of Surface Roughness due to Electrode Erosion in Field-Distortion Gas Switch

    NASA Astrophysics Data System (ADS)

    Liu, Xuandong; Wang, Hu; Li, Xiaoang; Zhang, Qiaogen; Wei, Jin; Qiu, Aici

    2013-08-01

    Field distortion gas switch is one of the crucial elements in a Marx generator, fast linear transformer driver and other pulsed power installations. The performance of the gas switch, which is dramatically affected by the surface roughness due to electrode erosion during the discharge process, directly influences the output parameters, stability and reliability of the pulsed power system. In this paper, an electrode surface roughness (ESR) calculation model has been established based on a great deal of experimental data under operating current. The discharge current waveform, the peak height of the burr, the radius and the depth of etch pits in the electrode erosion region were used to predict the ESR. Also, experimental results indicate that this calculation model can effectively estimate the ESR of the test gas switch.

  16. Enhanced charging kinetics of porous electrodes: surface conduction as a short-circuit mechanism.

    PubMed

    Mirzadeh, Mohammad; Gibou, Frederic; Squires, Todd M

    2014-08-29

    We use direct numerical simulations of the Poisson-Nernst-Planck equations to study the charging kinetics of porous electrodes and to evaluate the predictive capabilities of effective circuit models, both linear and nonlinear. The classic transmission line theory of de Levie holds for general electrode morphologies, but only at low applied potentials. Charging dynamics are slowed appreciably at high potentials, yet not as significantly as predicted by the nonlinear transmission line model of Biesheuvel and Bazant. We identify surface conduction as a mechanism which can effectively "short circuit" the high-resistance electrolyte in the bulk of the pores, thus accelerating the charging dynamics and boosting power densities. Notably, the boost in power density holds only for electrode morphologies with continuous conducting surfaces in the charging direction. PMID:25216005

  17. 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

  18. 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

  19. Adsorption of carboxymethylester-azobenzene on copper and gold single crystal surfaces

    NASA Astrophysics Data System (ADS)

    Piantek, M.; Miguel, J.; Bernien, M.; Navío, C.; Krüger, A.; Priewisch, B.; Rück-Braun, K.; Kuch, W.

    2008-11-01

    The adsorption of 3,3'-di(methoxycarbonyl)azobenzene (CMA) on Au(111) and on Cu(001) substrates was studied by X-ray absorption spectroscopy measurements at the C, N, and O K edges. We find the molecules physisorbed in a planar conformation flat on the Au(111) surface. At higher coverages, a molecular crystal is formed wherein the molecules have the same flat geometry. On Cu(001), additional chemical bonds are formed between the molecules and the surface via the nitrogen atoms. Here the methyl benzoate moieties are tilted out of the surface plane.

  20. 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

  1. 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.

  2. 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

  3. 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

  4. 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.

  5. 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

  6. Anodic Methods for Covalent Attachment of Ethynylferrocenes to Electrode Surfaces: Comparison of Ethynyl Activation Processes.

    PubMed

    Sheridan, Matthew V; Lam, Kevin; Sharafi, Mona; Schneebeli, Severin T; Geiger, William E

    2016-02-16

    The electrochemical oxidation of ferrocenes having an H- or Li-terminated ethynyl group has been studied, especially as it relates to their covalent anchoring to carbon surfaces. The anodic oxidation of lithioethynylferrocene (1-Li) results in rapid loss of Li(+) and formation of the ethynyl-based radical FeCp(η(5)-C5H4)(C≡C), (1, Cp = η(5)-C5H5), which reacts with the electrode. Chemically modified electrodes (CMEs) were thereby produced containing strongly bonded, ethynyl-linked monolayers and electrochemically controlled multilayers. Strong attachments of ethynylferrocenes to gold and platinum surfaces were also possible. The lithiation/anodic oxidation process is a mirror analogue of the diazonium/cathodic reduction process for preparation of aryl-modified CMEs. A second method produced an ethynylferrocene-modified electrode by direct anodic oxidation of the H-terminated ethynylferrocene (1-H) at a considerably more positive potential. Both processes produced robust modified electrodes with well-defined ferrocene-based surface cyclic voltammetry waves that remained unchanged for as many as 10(4) scans. Ferrocene derivatives in which the ethynyl moiety was separated from the cyclopentadienyl ring by an ether group showed very similar behavior. DFT calculations were performed on the relevant redox states of 1-H, 1-Li, and 1, with emphasis on the ferrocenyl vs ethynyl character of their high valence orbitals. Whereas the HOMOs of both 1-H and 1-Li have some ethynyl character, the SOMOs of the corresponding monocations are strictly ferrocenium in makeup. Predominant ethynyl character returns to the highest valence orbitals after loss of Li(+) from [1-Li](+) or loss of H(+) from [1-H](2+). These anodic processes hold promise for the controlled chemical modification of carbon and other electrode surfaces by a variety of ethynyl or alkynyl-linked organic and metal-containing systems. PMID:26756403

  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. Relating surface chemistry and oxygen surface exchange in LnBaCo2O(5+δ) air electrodes.

    PubMed

    Téllez, Helena; Druce, John; Kilner, John A; Ishihara, Tatsumi

    2015-01-01

    The surface and near-surface chemical composition of electroceramic materials often shows significant deviations from that of the bulk. In particular, layered materials, such as cation-ordered LnBaCo2O(5+δ) perovskites (Ln = lanthanide), undergo surface and sub-surface restructuring due to the segregation of the divalent alkaline-earth cation. These processes can take place during synthesis and processing steps (e.g. deposition, sintering or annealing), as well as at temperatures relevant for the operation of these materials as air electrodes in solid oxide fuel cells and electrolysers. Furthermore, the surface segregation in these double perovskites shows fast kinetics, starting at temperatures as low as 400 °C over short periods of time and leading to a decrease in the transition metal surface coverage exposed to the gas phase. In this work, we use a combination of stable isotope tracer labeling and surface-sensitive ion beam techniques to study the oxygen transport properties and their relationship with the surface chemistry in ordered LnBaCo2O(5+δ) perovskites. Time-of-Flight Secondary-Ion Mass Spectrometry (ToF-SIMS) combined with (18)O isotope exchange was used to determine the oxygen tracer diffusion (D*) and surface exchange (k*) coefficients. Furthermore, Low Energy Ion Scattering (LEIS) was used for the analysis of the surface and near surface chemistry as it provides information from the first mono-atomic layer of the materials. In this way, we could relate the compositional modifications (e.g. cation segregation) taking place at the electrochemically-active surface during the exchange at high temperatures and the oxygen transport properties in double perovskite electrode materials to further our understanding of the mechanism of the surface exchange process. PMID:26212446

  10. 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.

  11. Surface enhanced Raman scattering of new acridine based fluorophore adsorbed on silver electrode

    NASA Astrophysics Data System (ADS)

    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 Cd2+ ions to a system containing BHIA adsorbed on a silver electrode in equilibrium with the solution leads to the formation of BHIA/Cd2+ complex which desorption causes the loss of SERS signal.

  12. 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

  13. Surface structures, photovoltages, and stability of n-Si(111) electrodes surface modified with metal nanodots and various organic groups.

    PubMed

    Takabayashi, Susumu; Ohashi, Masato; Mashima, Kazushi; Liu, Yang; Yamazaki, Shoko; Nakato, Yoshihiro

    2005-09-13

    The surface structures, photovoltages, and stability of n-Si(111) electrodes surface-modified with Pt nanodots and organic groups were studied in an I-/I3- redox electrolyte, using alkyls of varied chain length and those having a double bond and ester at the terminal as the organic groups. The n-Si was first modified with the organic groups, and then Pt was electrodeposited on it. Linear sweep voltammetry revealed that, for the modification with alkyls, the overvoltage for the Pt deposition became significantly larger with increasing alkyl chain length, though this does not necessarily hold for the modification with alkyls having a double bond and ester. Scanning electron microscopic inspection showed that the Pt particle density decreased and the particle size increased, with increasing alkyl chain length. The photovoltaic characteristics and stability for the n-Si electrodes modified with the organic groups were much improved by the Pt nanodot coating, though they became somewhat inferior with increasing alkyl chain length. On the basis of these results, it is concluded that surface alkylation at high coverage together with coating with small Pt nanodots gives efficient and stable n-Si electrodes. PMID:16142967

  14. Influence of surface oxidation on ion dynamics and capacitance in porous and nonporous carbon electrodes

    DOE PAGESBeta

    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

  15. Mixed Azide-Terminated Monolayers: A Platform for Modifying Electrode Surfaces

    PubMed Central

    Collman, James P.; Devaraj, Neal K.; Eberspacher, Todd P. A.; Chidsey, Christopher E. D.

    2006-01-01

    We have prepared and characterized mixed self-assembled-monolayers (SAM) on gold electrodes from azido alkane thiols and various ω-functionalized alkane thiols. In the presence of copper(I) catalysts these azide-modified surfaces are shown to react rapidly and quantitatively with terminal acetylenes forming 1,2,3-triazoles, via “click” chemistry. The initial azide substituents can be identified and monitored using both grazing-angle infrared (IR) and X-ray photoelectron spectrosopies. Acetylenes possessing redox-active ferrocene substituents react with the azide-terminated mixed SAMs and electrochemical measurements of the ferrocene-modified SAM electrodes have been used to quantify the redox centers attached to these platforms. Time-resolved electrochemical measurements have enabled us to follow the formation of these ferrocene centers and thus to measure the rate of the surface “click” reaction. Under optimal conditions this well-behaved second-order reaction takes place with a rate constant of 1×103 M-1sec-1. Typical reaction times of several minutes were realized using micromolar concentrations of acetylene. These techniques have been used to construct well-characterized, covalently-modified monolayers that can be employed as functional electrode surfaces. PMID:16519441

  16. Mixed azide-terminated monolayers: a platform for modifying electrode surfaces.

    PubMed

    Collman, James P; Devaraj, Neal K; Eberspacher, Todd P A; Chidsey, Christopher E D

    2006-03-14

    We have prepared and characterized mixed self-assembled monolayers (SAM) on gold electrodes from azido alkane thiols and various omega-functionalized alkane thiols. In the presence of copper(I) catalysts, these azide-modified surfaces are shown to react rapidly and quantitatively with terminal acetylenes forming 1,2,3-triazoles, via "click" chemistry. The initial azide substituents can be identified and monitored using both grazing-angle infrared (IR) and X-ray photoelectron spectrosopies. Acetylenes possessing redox-active ferrocene substituents react with the azide-terminated mixed SAMs and electrochemical measurements of the ferrocene-modified SAM electrodes have been used to quantify the redox centers attached to these platforms. Time-resolved electrochemical measurements have enabled us to follow the formation of these ferrocene centers and thus to measure the rate of the surface "click" reaction. Under optimal conditions this well-behaved second-order reaction takes place with a rate constant of 1 x 10(3) M(-)(1) s(-)(1). Typical reaction times of several minutes were realized using micromolar concentrations of acetylene. These techniques have been used to construct well-characterized, covalently modified monolayers that can be employed as functional electrode surfaces. PMID:16519441

  17. 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

  18. Understanding surface reactivity of Si electrodes in Li-ion batteries by in operando scanning electrochemical microscopy.

    PubMed

    Ventosa, E; Wilde, P; Zinn, A-H; Trautmann, M; Ludwig, A; Schuhmann, W

    2016-05-21

    In operando SECM is employed to monitor the evolution of the electrically insulating character of a Si electrode surface during (de-)lithiation. The solid-electrolyte interface (SEI) formed on Si electrodes is shown to be intrinsically electrically insulating. However, volume changes upon (de-)lithiation lead to the loss of the protecting character of the initially formed SEI. PMID:27136966

  19. 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

  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 PAGESBeta

    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-enhanced resonance hyper-Raman scattering and surface-enhanced resonance Raman scattering of dyes adsorbed on silver electrode and silver colloid: a comparison study

    NASA Astrophysics Data System (ADS)

    Li, Wu-Hu; Li, Xiao-Yuan; Yu, Nai-Teng

    1999-10-01

    Surface-enhanced resonance hyper-Raman scattering (SERHRS) and surface-enhanced resonance Raman scattering (SERRS) of three dyes, rhodamine 6G, crystal violet and basic fuchsin, are studied comparatively on electrochemically roughened silver electrode and silver colloid, respectively. All three dyes show a better SERHRS efficiency on the silver colloid than on the silver electrode, a phenomenon just opposite to what we have recently observed for pyridine and pyrazine [Chem. Phys. Lett. 305 (1999) 303]. These results suggest that the efficiency of SEHRS depends not only on the active surfaces employed (colloidal metals versus roughened electrodes) but also on the types of the adsorbed molecules.

  5. A novel procedure for rapid surface functionalisation and mediator loading of screen-printed carbon electrodes.

    PubMed

    Pchelintsev, Nikolay A; Millner, Paul A

    2008-04-01

    We report a simple and rapid procedure that leads to incorporation of mediator and introduction of amine functionality onto the surface of screen-printed carbon electrodes (SPCE). The electrodes were doped with cobalt phthalocyanine (CoPc) by enhanced adsorption in a process that uses minimal amounts of this redox mediator as compared with CoPc loaded inks. The CoPc-doped SPCE showed a substantially increased sensitivity to hydrogen peroxide and thiocholine as compared to unmodified electrodes. This greatly facilitated their use as transducers for the construction of amperometric biosensors based on enzymes producing oxidizable products such as hydrogen peroxide or thiols. Immobilisation of enzymes including glucose oxidase, acetylcholinesterase and choline oxidase was achieved through their multi-contact electrostatic interaction with polyethyleneimine (PEI) which was electrodeposited on the surface of CoPc-doped electrodes in one step from ethanolic solution. The efficiency of enzyme immobilisation was shown to depend on the molecular weight of the PEI used, reaching a maximum for 25 kDa PEI. The biosensors shown sensitivity to glucose at 130 nA mM(-1) (LOD 0.15 mM) and to acetylcholine at 70 nA mM(-1) (LOD 0.10mM) under +0.6 V. Detection of glucose has been demonstrated at +0.4V with the sensitivity of 60 nA mM(-1) and LOD of 0.33 mM. Possibility of the inhibition analysis of pesticides has been shown for acetylcholinesterase-based sensors. PMID:18358865

  6. 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.

  7. 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. PMID:27189079

  8. Surface Enhanced Infrared Studies of 4-Methoxypyridine Adsorption on Gold Film Electrodes.

    PubMed

    Quirk, Amanda; Unni, Bipinlal; Burgess, Ian J

    2016-03-01

    This work uses electrochemical surface sensitive vibrational spectroscopy to characterize the adsorption of a known metal nanoparticle stabilizer and growth director, 4-methoxypyridine (MOP). Surface enhanced infrared absorption spectroscopy (SEIRAS) is employed to study the adsorption of 4-methoxypyridine on gold films. Experiments are performed under electrochemical control and in different electrolyte acidities to identify both the extent of protonation of the adsorbed species as well as its orientation with respect to the electrode surface. No evidence of adsorbed conjugated acid is found even when the electrolyte pH is considerably lower than the pKa. Through an analysis of the transition dipole moments, determined from DFT calculations, the SEIRA spectra support an adsorption configuration through the ring nitrogen which is particularly dominant in neutral pH conditions. Adsorption is dependent on both the electrical state of the Au film electrode as well as the presence of ions in the electrolyte that compete for adsorption sites at positive potentials. Combined differential capacitance measurements and spectroscopic data demonstrate that both a horizontal adsorption geometry and a vertical adsorption phase can be induced, with the former being found on negatively charged surfaces in acidic media and the latter over a wide range of polarizations in neutral solutions. PMID:26862774

  9. Surface passivation of natural graphite electrode for lithium ion battery by chlorine gas.

    PubMed

    Suzuki, Satoshi; Mazej, Zoran; Zemva, Boris; Ohzawa, Yoshimi; Nakajima, Tsuyoshi

    2013-01-01

    Surface lattice defects would act as active sites for electrochemical reduction of propylene carbonate (PC) as a solvent for lithium ion battery. Effect of surface chlorination of natural graphite powder has been investigated to improve charge/discharge characteristics of natural graphite electrode in PC-containing electrolyte solution. Chlorination of natural graphite increases not only surface chlorine but also surface oxygen, both of which would contribute to the decrease in surface lattice defects. It has been found that surface-chlorinated natural graphite samples with surface chlorine concentrations of 0.5-2.3 at% effectively suppress the electrochemical decomposition of PC, highly reducing irreversible capacities, i.e. increasing first coulombic efficiencies by 20-30% in 1 mol L-1 LiClO4-EC/DEC/PC (1:1:1 vol.). In 1 mol L-1 LiPF6-EC/EMC/PC (1:1:1 vol.), the effect of surface chlorination is observed at a higher current density. This would be attributed to decrease in surface lattice defects of natural graphite powder by the formation of covalent C-Cl and C=O bonds. PMID:24169705

  10. Acetylcholinesterase-based biosensor electrodes for organophosphate pesticide detection. I. Modification of carbon surface for immobilization of acetylcholinesterase.

    PubMed

    Vakurov, A; Simpson, C E; Daly, C L; Gibson, T D; Millner, P A

    2004-12-15

    Screen-printed carbon electrodes modified with the dialdehydes, glutaraldehyde and terephthaldicarboxaldehyde, and then polyethyleneimine have been utilized for production of pesticide biosensors based on acetylcholinesterase. To improve the extent of dialdehyde modification, the electrodes were NH2-derivatized, initially by electrochemical reduction of 4-nitrobenzenediazonium to a nitroaryl radical permitting attachment to the carbon surface. Subsequent reduction of the 4-nitrobenzene yields a 4-aminobenzene modified carbon surface. Drosophila melanogaster acetylcholinesterase was immobilized either covalently onto dialdehyde modified electrodes or non-covalently onto polyethyleneimine modified electrodes. Internal diffusion limitations due to the dialdehyde and polyethyleneimine modifications increased the apparent Km of the immobilized enzyme. The thiocholine sensitivity was about 90% for dialdehyde modified electrodes and about 10% for polyethyleneimine modified electrodes as compared with non-modified carbon electrodes. The detection limit of the biosensors produced by non-covalent immobilization of acetylcholinesterase onto polyethyleneimine modified carbon electrodes was found to be about 10(-10) M for the organophosphate pesticide dichlorvos. PMID:15556357

  11. 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. PMID:21678586

  12. 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.

  13. Robust myoelectric signal detection based on stochastic resonance using multiple-surface-electrode array made of carbon nanotube composite paper

    NASA Astrophysics Data System (ADS)

    Shirata, Kento; Inden, Yuki; Kasai, Seiya; Oya, Takahide; Hagiwara, Yosuke; Kaeriyama, Shunichi; Nakamura, Hideyuki

    2016-04-01

    We investigated the robust detection of surface electromyogram (EMG) signals based on the stochastic resonance (SR) phenomenon, in which the response to weak signals is optimized by adding noise, combined with multiple surface electrodes. Flexible carbon nanotube composite paper (CNT-cp) was applied to the surface electrode, which showed good performance that is comparable to that of conventional Ag/AgCl electrodes. The SR-based EMG signal system integrating an 8-Schmitt-trigger network and the multiple-CNT-cp-electrode array successfully detected weak EMG signals even when the subject’s body is in the motion, which was difficult to achieve using the conventional technique. The feasibility of the SR-based EMG detection technique was confirmed by demonstrating its applicability to robot hand control.

  14. 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

  15. Calcium phosphates deposited on titanium electrode surface--part 1: Effect of the electrode polarity and oxide film on the deposited materials.

    PubMed

    Okawa, Seigo; Watanabe, Kouichi; Kanatani, Mitsugu

    2013-01-01

    We report experimental results about the effect of polarity of electrode and anodized titanium oxide film on the deposited materials by electrolysis of an acidic calcium phosphate solution. Mirror-polished titanium and anodized titanium were used as anode or cathode, and a Pt plate was used as a counter electrode. The load voltage was held constant at 20 VDC. No deposited materials were found on the anode surface. On the other hand, dicalcium phosphate dihydrate (DCPD) was deposited on the cathode surface at the beginning of the electrolysis. After the electrolysis time 600 s, the non-stoichiometric hydroxyapatite (HAp) with several hundred nanometers was formed on the specimen surface. Based on X-ray photoelectron spectroscopy data, the anodized oxide film contained both P(5+) and P(3+) ions. This characteristic of the oxide film and the electrolysis conditions were related to the behavior of the deposition of ultra fine HAp with high crystallinity. PMID:23538764

  16. 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

  17. Surface Modification of Silver Nanowires for Morphology and Processing Control in Composite Transparent Electrodes.

    PubMed

    Liang, Zhiming; Graham, Kenneth R

    2015-10-01

    Silver nanowires are attractive components for a number of materials and applications, including silver nanowire (AgNW)-polymer composites, electrically conductive coatings, and transparent electrodes. In this manuscript, the ability of thiols with hydrophobic to ionic end groups to bind to AgNW surfaces is investigated, followed by how the polarity of the surface modifying thiol influences the morphological and electrical properties of both AgNW/PEDOT:PSS blend films and pure AgNW networks. Utilizing surface modification of AgNWs with sodium 3-mercapto-1-propanesulfonate (MPS), morphologically homogeneous AgNW/PEDOT:PSS thin films with an order of magnitude lower sheet resistance at similar transmittance values than unmodified AgNWs are obtained with a one-step processing method. Brief optimization of MPS-AgNW/PEDOT:PSS blends yields a sheet resistance of 22.6 Ω/□ at 81.4% transmittance. PMID:26389535

  18. 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.

  19. Determination of photoelectrochemical water oxidation intermediates on haematite electrode surfaces using operando infrared spectroscopy.

    PubMed

    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 Fe(IV)=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. PMID:27442283

  20. Current distribution over the electrode surface in a lead-acid cell during discharge

    NASA Astrophysics Data System (ADS)

    Král, Petr; Křivák, Petr; Bača, Petr; Calábek, Milan; Micka, Karel

    The current distribution over the plate surface in lead-acid cells in the course of discharge was determined mathematically by using the equivalent circuit method. The dependence of the internal cell resistance on the current and charge passed was determined by measurements on a laboratory cell. Six cell variants were considered differing by the location of tabs serving as current terminals. The results are presented in the form of 3D diagrams at various states of discharge. To make the current distribution nearly uniform, extended current tabs located at opposite ends of the plate electrodes were proposed.

  1. Single molecule dissociation by tunneling electrons in NO-Co-Porphyrin complex on Au(111): A novel mechanics revealed by scanning tunneling spectroscopy and first-principles thermodynamic simulation

    NASA Astrophysics Data System (ADS)

    Chang, Yunhee; Kim, Howon; Lee, Eui-Sup; Jang, Won-Jun; Kim, Yong-Hyun; Kahng, Se-Jong

    2015-03-01

    To microscopically understand the mechanisms of electron-induced NO dissociations, we performed first-principles density-functional theory (DFT) calculations for NO-CoTPP on Au(111). We explain the scanning tunneling microscopy (STM) results that the dissociations of NO were induced by both positive and negative voltage pulses with threshold voltages, +0.68 V and 0.74 V, respectively, at 0.1 nA tunneling current, showing power law relations between tunneling current and dissociation yield. To evaluate first-principles thermodynamics of the NO dissociation, we considered not only adsorption-desorption energetics, zero-point energy, and vibrational free energy at experiment temperature from first-principles, but also the chemical potential of NO gas at the cryogenic ultra-high vacuum condition. Using first-principles thermodynamics for the NO dissociation, we argue that the dissociations are induced with inelastic electron tunneling through molecular orbital resonances.

  2. The influence of orientations and external electric field on charge carrier mobilities in CuPc and F16CuPc films on highly ordered pyrolytic graphite and octane-1-thiol terminated Au(111) substrates.

    PubMed

    Chen, Shuang; Ma, Jing

    2010-10-14

    The lying-down and standing-up CuPc and F(16)CuPc films on HOPG (highly ordered pyrolytic graphite) and C8-SAM/Au(111) (octane-1-thiol terminated Au(111)) substrates are investigated by using a hybrid strategy combing the molecular dynamic (MD) simulations with density functional theory (DFT) calculations, in order to understand the influence of packing orientation on charge carrier mobilities. On the basis of the periodic slab model and consistent-valence force field, MD simulations show the populations of various packing configurations and radial distribution of intermolecular distance in the films at room temperature. It is also demonstrated that the external electric field (parallel or perpendicular to the substrate) perturbs the intermolecular distances in CuPc and F(16)CuPc films, especially for the slipped edge-to-face stackings. DFT calculations are then used to evaluate two key charge-transfer parameters, reorganization energy and transfer integral. An electrostatics embedding model is employed to approximately consider the external electrostatics contributions to reorganization energy. The thermal-averaged mobility is consequently estimated by taking account of both electronic structures of charge-hopping pairs and dynamic fluctuations in film morphologies under various experimental conditions. It is found that CuPc has smaller reorganization energy and larger hole (electron) mobilities than F(16)CuPc. Under the external electric field of 10(4)-10(7) V cm(-1), both hole and electron mobilities of CuPc and F(16)CuPc films would decrease to 1-3 orders of magnitude. CuPc (F(16)CuPc) films show substantial orientation dependence of mobilities on the ratio of standing-up versus lying-down orientations falling in the range of 10-1000. PMID:20714578

  3. 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.

  4. 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. PMID:26241969

  5. A flexible optimization method for scaling surface-electrode ion traps

    NASA Astrophysics Data System (ADS)

    Liu, Wei; Chen, Shuming; Wu, Wei

    2014-12-01

    Recent advances in scaling surface-electrode ion trap have demonstrated optimization of critical components, such as junctions and loading slots. In this study, a flexible method to systematically optimize the shape of radio frequency (rf) rails in different components was proposed. The rf rails were discretized in the electrostatic calculation; thus, the spatial fields of different components can be accumulated according to the superposition principle. The optimization process was accomplished by placing artificial control points along the edges of the rf rails, providing controllable degree of freedom. The locations of these control points were modified using ant colony optimization, which employs a proposed hybrid multi-objective function. The proposed method was verified with three kinds of components: an X junction, a Y junction, and a loading slot. Compared with the results obtained using non-optimized cases and the existing methods, the proposed method produced favorable results in maintaining the ion height and minimizing the axial pseudopotential barrier and rf noise heating. The proposed method can also be used to optimize other scaling components of surface-electrode ion traps.

  6. 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.

  7. Surface chemistry study of RuO2/IrO2/TiO2 mixed-oxide electrodes.

    PubMed

    Barison, Simona; Daolio, Sergio; Fabrizio, Monica; De Battisti, Achille

    2004-01-01

    DSA metal oxide electrodes such as the RuO(2)/IrO(2)/TiO(2) mixed system are widely studied for their excellent electrocatalytic activity. In order to understand their catalytic properties, the comprehension of the surface chemistry involved during electrochemical treatments is crucial. With this aim, RuO(2)/IrO(2)/TiO(2) mixed-oxide electrodes having various noble metal contents were studied by means of secondary ion mass spectrometry (SIMS). In particular, cathodic and anodic polarization and O(2) evolution reactions were carried out to test the electrode behaviour and SIMS analyses were performed after all these treatments. In this way, surface changes induced by electrochemical treatments and depending on electrode composition were widely investigated by SIMS, revealing, for example, the presence of hydration or preferential dissolution phenomena induced by electrochemical processing. PMID:14755612

  8. Improvements in MDC and TWT overall efficiency through the application of carbon electrode surfaces. [Multistage Depressed Collectors

    NASA Technical Reports Server (NTRS)

    Ramins, Peter; Ebihara, Ben T.

    1986-01-01

    The effects of secondary electron emission losses on TWT efficiency are investigated and techniques for minimizing these losses are described. The TWT-multistage depressed collector performance was optimized and measured over a wide range of operating conditions using geometrically identical collectors that utilized copper, pyrolytic graphite, and isotropic graphite electrodes. The data reveal that carbon rather than copper electrodes improve the TWT efficiency, and the ion-textured graphite is most effective in minimizing the secondary electron emission losses. It is noted that degradation of the collector efficiency can be limited to a small percentage with the proper MDC design and the use of low secondary electron yield carbon electrode surfaces.

  9. 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

  10. Surface-electrode decelerator and deflector for Rydberg atoms and molecules

    NASA Astrophysics Data System (ADS)

    Allmendinger, P.; Deiglmayr, J.; Agner, J. A.; Schmutz, H.; Merkt, F.

    2014-10-01

    A surface-electrode decelerator and deflector for Rydberg atoms and molecules has been developed with the goal of performing collisional experiments. Translationally cold H2 molecules in a supersonic beam were excited to Rydberg-Stark states of principal quantum number n =31, loaded into electric traps moving at a predetermined speed above the surface of a bent printed circuit board, decelerated, and deflected from the original direction of the supersonic beam by an angle of 10∘. The phase-space characteristics of the deflected beam were characterized by measuring the time-of-flight distribution and images of the Rydberg molecules and comparing them to the results of numerical particle-trajectory simulations. More than 1000 H2 molecules were deflected per experimental cycle at a repetition rate of 25 Hz. The phase-space characteristics of the deflector make it attractive to study ion-molecule reactions at low collision energies.

  11. 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.

  12. Electromechanical model for a self-sensing ionic polymer-metal composite actuating device with patterned surface electrodes

    NASA Astrophysics Data System (ADS)

    Kruusamäe, Karl; Brunetto, Paola; Punning, Andres; Kodu, Margus; Jaaniso, Raivo; Graziani, Salvatore; Fortuna, Luigi; Aabloo, Alvo

    2011-12-01

    This paper further discusses a concept of creating a self-sensing ionic polymer-metal composite (IPMC) actuating device with patterned surface electrodes where the actuator and sensor elements are separated by a grounded shielding electrode. Different patterning methods are discussed and compared in detail; the presented experimental data give an understanding of the qualitative properties of the patterns created. Finally, an electromechanical model of the device is proposed and validated.

  13. 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.

  14. 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].

  15. 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.

  16. 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 1-500nM of linearity range was obtained. PMID:26992524

  17. Evaluation of electrode surface modification techniques for the development of chemical sensors

    SciTech Connect

    Galiatsatos, C.

    1988-01-01

    This thesis covers several aspects of electrode surface modification techniques. The successful application of gamma-radiation to create polymer-coated electrodes, where the polymers can be ion exchangers and consequently of great analytical interest by themselves (such as the polymer poly(diallyl) dimethyl ammonium chloride) or where some other neutral polymers can function as convenient matrices for the introduction of biomolecules and/or other electrochemically interesting species is reported. This is demonstrated by using the neutral polymer poly(vinyl alcohol) (PVAL) as a matrix for immobilization of the enzyme glucose oxidase and the mediator methyl viologen. The effect of {gamma}-radiation on PVAL is discussed, as well as swelling properties of the irradiated polymers and specific characteristics of the created chemical sensors. Results of an experiment where the various kinds of interactions between the ion-exchange polymer Nafion and some positively charged species are explored are reported, and a model system for competition (methyl viologen vs. ruthenium hexaamine) which increases significantly our understanding of the interaction is mentioned. The effect of {gamma}-radiation on Nafion and its ion-exchange compabilities is discussed also. A system of conduction polymers primarily polypyrrole, used as a detector of electroinactive anions due to their doping-undergoing in the film is discussed. Preliminary results on a new method that involves chemical cross-linking of a triisocyane molecule with -OH containing polymers in the presence of enzymes are reported.

  18. 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.

  19. The ensemble effect of formic acid oxidation on platinum-gold electrode studied by first-principles calculations

    NASA Astrophysics Data System (ADS)

    Zhong, Wenhui; Qi, Yuanyuan; Deng, Mingsen

    2015-03-01

    The reaction mechanisms for HCOOH oxidation on a series of PtAu(111) alloy surfaces in the aqueous solution phase are investigated by density functional theory calculations. It is found that the dehydrogenation pathway of HCOOH oxidation occurs through the formation of formate with a barrier of 16.8 kcal mol-1 and requires at least one Pt atom on the surface. In contrast, the CO formation pathway proceeds through the dimerization with a barrier of 5.6 kcal mol-1, for which at least three Pt atoms with a non-equilateral structure are required. The calculated average electrostatic potential, charge density difference, Bader charge and partial density of states all show obvious charge transfer from the alloy surface Pt atoms to HCOOH molecules, indicating that Pt sites are the reaction active center. Different ensemble of Pt sites on PtAu(111) surfaces can have significant impact on the catalysis performance for HCOOH oxidation. The non-equilateral Pt site upon PtAu(111) should be avoided to eliminate CO poisoning effect on Pt-based catalysts.

  20. Study of the adsorbed layer on a solid electrode surface by specular reflection measurement

    NASA Astrophysics Data System (ADS)

    Kusu, Fumiyo; Takamura, Kiyoko

    1985-07-01

    Specular reflection measurements were carried out to study the adsorbed layers of certain heterocyclic compounds such as adenine, barbital, 2'-deoxyadenosine, phenobarbital, pyridine and thymine. When pyridine was present in 0.1M NaClO 4, a marked decrease in the reflectivity of a gold electrode was observed. In the potential range near the point of zero charge on the reflectivity-potential curve, the decrease was due to the adsorption of pyridine. Assuming the reflectivity change to be proportional to the surface coverage, the potential and concentration dependence of pyridine adsorption was determined and analysed on the basis of a Langmuir-type adsorption isotherm. The refractive indices and extinction coefficients for the adsorbed layers of the compounds investigated were evaluated using the observed reflectivity change, according to relations proposed by McIntyre and Aspnes.

  1. 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.

  2. 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

  3. Experimental progress with novel surface electrode ion trap structures for quantum information processing

    NASA Astrophysics Data System (ADS)

    Clark, Craig; Blain, Matthew; Benito, Francisco; Chou, Chin-Wen; Descour, Mike; Ellis, Rob; Haltli, Ray; Heller, Edwin; Kemme, Shanalyn; Sterk, Jon; Tabakov, Boyan; Tigges, Chris; Maunz, Peter; Stick, Daniel

    2013-05-01

    Segmented surface electrode ion traps are one of the most mature platforms among candidates for scalable quantum information processing. In this poster, an overview of current results from four specific projects will be presented. Two projects involve increased light collection from trapped ion for state detection and/or remote entangling of distant ions. The first involves cavity integration into a linear surface trap, and the second, involves integration of diffractive optical elements into a linear surface trap for increased light collection. Another project involves a trap with a ring geometry which could be used to trap long chains of equally spaced ions. Finally, we report on initial testing of a trap structure with vastly improved in-plane optical access. In this structure in-plane beams can be focused to less than 8 microns while keeping a distance of at least 5 beam radii to the trap structure. Along with these projects other relevant progress from Sandia National Laboratory's ion trap group will be presented. This work was supported by Sandia's Laboratory Directed Research and Development (LDRD) and the Intelligence Advanced Research Projects Activity (IARPA). Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the US Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  4. 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

  5. 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

  6. 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

  7. Effect of surface fluorination on the electrochemical and photoelectrocatalytic properties of nanoporous titanium dioxide electrodes.

    PubMed

    Monllor-Satoca, Damián; Lana-Villarreal, Teresa; Gómez, Roberto

    2011-12-20

    Titanium dioxide is a widely used photocatalyst whose properties can be modified by fluoride adsorption. This work is focused on the effect of surface fluorination on the electrochemical and photoelectrocatalytic properties of TiO(2) nanoporous thin films. Surface fluorination was achieved by simple addition of HF to the working solution (pH 3.5). Open circuit potential as well as ex situ XPS measurements verify that surface modification takes place. Fluorination triggers a significant capacitance increase in the accumulation potential region, as revealed by dark voltammetric measurements for all the TiO(2) samples studied. The photoelectrocatalytic properties (measured as photocurrents under white light illumination) depend on the substrate being oxidized and, in some cases, on the nature of the TiO(2) sample. In particular, the results obtained for electrodes prepared with a mixed phase (rutile + anatase) commercial nanopowder (PI-KEM) indicate that the processes mediated by surface trapped holes, such as the photooxidation of water or methanol, are accelerated while those occurring by direct hole capture from the adsorbed state (formic acid) are retarded. The photooxidation of catechol and phenol is also enhanced upon fluorination. In such a case, the effect can be rationalized on the basis of a diminished recombination and a surface displacement of both the oxidizable organic substrates and the poisoning species formed as a result of the organics oxidation. Photoelectrochemical and in situ infrared spectroscopic measurements support these ideas. In a more general vein, the results pave the way toward a better understanding of the photocatalysis phenomena, unravelling the importance of the reactant adsorption processes. PMID:22039955

  8. Gas cluster ion beam surface treatments for reducing field emission and breakdown of electrodes and SRF cavities.

    SciTech Connect

    Swenson, D. R.; Wu, A. T.; Degenkolb, E.; Insepov, Z.; Mathematics and Computer Science; Epion Corp.; Jefferson National Lab.

    2007-01-01

    Sub-micron-scale surface roughness and contamination cause field emission that can lead to high-voltage breakdown of electrodes, and these are limiting factors in the development of high gradient RF technology. We are studying various Gas Cluster Ion Beam (GCIB) treatments to smooth, clean, etch and/or chemically alter electrode surfaces to allow higher fields and accelerating gradients, and to reduce the time and cost of conditioning high-voltage electrodes. For this paper, we have processed Nb, stainless steel and Ti electrode materials using beams of Ar, O{sub 2}, or NF{sub 3} + O{sub 2} clusters with accelerating potentials up to 35 kV. Using a scanning field emission microscope (SFEM), we have repeatedly seen a dramatic reduction in the number of field emission sites on Nb coupons treated with GCIB. Smoothing effects on stainless steel and Ti substrates, evaluated using SEM and AFM imaging, show that 200-nm-wide polishing scratch marks are greatly attenuated. A 150-mm diameter GCIB-treated stainless steel electrode has shown virtually no DC field emission current at gradients over 20 MV/m.

  9. 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.

  10. Voltage breakdown between closely spaced electrodes over polymeric insulator surfaces in air

    NASA Astrophysics Data System (ADS)

    Gray, Eoin W.; Harrington, Daniel J.

    1982-01-01

    Voltage breakdowns of some narrow gap electrodes [2-10 mil (0.05-0.25 mm)] on polymeric insulator surfaces (epoxy-glass and triazine) have been examined over the pressure range from atmospheric pressure to 127 Torr and are shown to be an air breakdown modified by the presence of the insulator. Breakdown values as a function of the number of the breakdown and discharge energy level were also examined. In the worst case the breakdown voltage was observed to decrease by approximately 1300 V after about five successive breakdowns. The breakdown voltage between narrowly spaced metallic contacts on dielectric surfaces has been assumed to exhibit a Gaussian distribution. Non-Gaussian, bimodal distributions have been observed in the present work. These bimodal distributions, found on fine line epoxy-glass and triazine printed wiring boards, and attempts for explanation in terms of the flashover discharge initiating mechanisms, including the effects of ultraviolet radiation and a negative-ion flux on breakdown, are described. Negative ions appear to reduce the standard deviation but do not reduce the breakdown voltage. Ultraviolet radiation reduces both the standard deviation and the breakdown voltage. Increasing the conductor overlap distance (line length) reduced the breakdown voltage.

  11. 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).

  12. Surface-treated carbon electrodes with modified potential of zero charge for capacitive deionization.

    PubMed

    Wu, Tingting; Wang, Gang; Zhan, Fei; Dong, Qiang; Ren, Qidi; Wang, Jianren; Qiu, Jieshan

    2016-04-15

    The potential of zero charge (Epzc) of electrodes can greatly influence the salt removal capacity, charge efficiency and cyclic stability of capacitive deionization (CDI). Thus optimizing the Epzc of CDI electrodes is of great importance. A simple strategy to negatively shift the Epzc of CDI electrodes by modifying commercial activated carbon with quaternized poly (4-vinylpyridine) (AC-QPVP) is reported in this work. The Epzc of the prepared AC-QPVP composite electrode is as negative as -0.745 V vs. Ag/AgCl. Benefiting from the optimized Epzc of electrodes, the asymmetric CDI cell which consists of the AC-QPVP electrode and a nitric acid treated activated carbon (AC-HNO3) electrode exhibits excellent CDI performance. For inverted CDI, the working potential window of the asymmetric CDI cell can reach 1.4 V, and its salt removal capacity can be as high as 9.6 mg/g. For extended voltage CDI, the salt removal capacity of the asymmetric CDI cell at 1.2/-1.2 V is 20.6 mg/g, which is comparable to that of membrane CDI using pristine activated carbon as the electrodes (19.5 mg/g). The present work provides a simple method to prepare highly positively charged CDI electrodes and may pave the way for the development of high-performance CDI cells. PMID:26878480

  13. [Rapid simulation of electrode surface treatment based on Monte-Carlo model].

    PubMed

    Hu, Zhengtian; Xu, Ying; Guo, Miao; Sun, Zhitong; Li, Yan

    2014-12-01

    Micro- and integrated biosensor provides a powerful means for cell electrophysiology research. The technology of electroplating platinum black on the electrode can uprate signal-to-noise ratio and sensitivity of the sensor. For quantifying analysis of the processing method of electroplating process, this paper proposes a grid search algorithm based on the Monte-Carlo model. The paper also puts forward the operational optimization strategy, which can rapidly implement the process of large-scale nanoparticles with different particle size of dispersion (20-200 nm) attac- hing to the electrode and shortening a simulation time from average 20 hours to 0.5 hour when the test number is 10 and electrode radius is 100 microm. When the nanoparticle was in a single layer or multiple layers, the treatment uniformity and attachment rate was analyzed by using the grid search algorithm with different sizes and shapes of electrode. Simulation results showed that under ideal conditions, when the electrode radius is less than 100 /m, with the electrode size increasing, it has an obvious effect for the effective attachment and the homogeneity of nanoparticle, which is advantageous to the quantitative evaluation of electrode array's repeatability. Under the condition of the same electrode area, the best attachment is on the circular electrode compared to the attachments on the square and rectangular ones. PMID:25868260

  14. Laminar flow-based micro fuel cell utilizing grooved electrode surface

    NASA Astrophysics Data System (ADS)

    Ha, Seung-Mo; Ahn, Yoomin

    2014-12-01

    Microfluidic fuel cells have low power density and poor fuel utilization due to the generation of a reaction depletion zone. In this study, cell electrodes patterned with grooves are proposed for passive control of the depletion zone, where a secondary transport flow over the grooved electrode replenishes the depleted layers. The proposed membrane-less fuel cell is composed of a polydimethylsiloxane layer over a photoresist microchannel wall and a glass substrate that contains platinum electrodes. The optimum gap between the electrodes and the height of grooves are designed based on a computational fluid dynamics simulation. Hydrogen peroxide is used both as a fuel (when it is mixed with sodium hydroxide) and as an oxidant (when it is mixed with sulfuric acid). During the experiments, electrodes of various lengths are integrated on the bottom of the Y-channel. Experimental results show that the effect of grooves on cell performance is independent of fuel rate and fuel concentration, but the effect is remarkable when the length of the electrode is large. The peak power density with grooved electrodes improves by a maximum of 13.93% compared to that of planar electrodes. This grooved electrode-based fuel cell is expected to be a useful microdevice for power generation.

  15. On-Surface Cross Coupling Methods for the Construction of Modified Electrode Assemblies with Tailored Morphologies †

    PubMed Central

    Gietter, Amber A. S.; Pupillo, Rachel C.; Yap, Glenn P. A.; Beebe, Thomas P.

    2014-01-01

    Controlling the molecular topology of electrode–catalyst interfaces is a critical factor in engineering devices with specific electron transport kinetics and catalytic efficiencies. As such, the development of rational methods for the modular construction of tailorable electrode surfaces with robust molecular wires (MWs) exhibiting well-defined molecular topologies, conductivities and morphologies is critical to the evolution and implementation of electrochemical arrays for sensing and catalysis. In response to this need, we have established modular on-surface Sonogashira and Glaser cross-coupling processes to synthetically install arrays of ferrocene-capped MWs onto electrochemically functionalized surfaces. These methods are of comparable convenience and efficiency to more commonly employed Huisgen methods. Furthermore, unlike the Huisgen reaction, this new surface functionalization chemistry generates modified electrodes that do not contain unwanted ancillary metal binding sites, while allowing the bridge between the ferrocenyl moiety and electrode surface to be synthetically tailored. Electrochemical and surface analytical characterization of these platforms demonstrate that the linker topology and connectivity influences the ferrocene redox potential and the kinetics of charge transport at the interface. PMID:25520772

  16. 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

  17. Displacement of thiophene by methanethiol observed in situ by scanning tunneling microscopy and quartz crystal oscillator gravimetric analysis on Au(111)

    SciTech Connect

    Dishner, M.H.; Taborek, P.; Hemminger, J.C.; Feher, F.J.

    1998-11-10

    Quartz crystal microbalance and scanning tunneling microscopy experiments have been used to demonstrate that self-assembled monolayers of thiophene on gold can be quantitatively replaced by absorption of methanethiol from the gas phase. Adsorption of thiophene on the gold surface results in the relaxation of the clean gold surface reconstruction and the formation of vacancy islands or pits in the gold. Subsequent annealing of the monolayer can result in the complete removal of the vacancy islands. Methanethiol displacement of thiophene monolayers that have been previously annealed to remove vacancy island pits does not generate additional pits in the gold surface. Thus, ordered methanethiol monolayers which are free from vacancy island pits in the underlying gold surface can be formed by displacement of annealed thiophene monolayers. These results provide strong additional evidence that the formation of vacancy islands in the gold during the formation of alkanethiol SAMs is directly associated with relaxation of the clean surface reconstruction, rather than conventional chemical etching of the surface by alkanethiol.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Phytochelatin Modified Electrode Surface as a Sensitive Heavy-Metal Ion Biosensor

    PubMed Central

    Adam, Vojtech; Zehnalek, Josef; Petrlova, Jitka; Potesil, David; Sures, Bernd; Trnkova, Libuse; Jelen, Frantisek; Vitecek, Jan; Kizek, Rene

    2005-01-01

    Electrochemical biosensors have superior properties over other existing measurement systems because they can provide rapid, simple and low-cost on-field determination of many biological active species and a number of dangerous pollutants. In our work, we suggested a new heavy metal biosensor based on interaction of heavy metal ions (Cd2+ and Zn2+) with phytochelatin, which was adsorbed on the surface of the hanging mercury drop electrode, using adsorptive transfer stripping differential pulse voltammetry. In addition, we applied the suggested technique for the determination of heavy metals in a biological sample – human urine and platinum in a pharmaceutical drug. The detection limits (3 S/N) of Cd(II), Zn(II) and cis-platin were about 1.0, 13.3 and 1.9 pmole in 5 μl, respectively. On the basis of the obtained results, we propose that the suggested technique offers simple, rapid, and low-cost detection of heavy metals in environmental, biological and medical samples.

  4. Morphology-dependent NiO modified glassy carbon electrode surface for lead(II) and cadmium(II) detection

    NASA Astrophysics Data System (ADS)

    Li, Xuewu; Wen, Hao; Fu, Qiang; Peng, Dai; Yu, Jingui; Zhang, Qiaoxin; Huang, Xingjiu

    2016-02-01

    Glassy carbon electrode (GCE) surfaces have been modified with different NiO morphologies consisting of rods NiO, flakes NiO and balls NiO prepared via the hydrothermal synthesis method for Pb(II) and Cd(II) detection by using the square wave anodic stripping voltammetry (SWASV). Meanwhile, the typical cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), BET surface area and adsorption property of the modified electrode surfaces have been investigated to evaluate their electrochemical detection effect. Results show that balls NiO modified GCE can get the optimal detection ability for its highest detection sensitivity to Pb(II) (13.46 A M-1) and Cd(II) (5.10 A M-1), the lowest detection limit (DL) to Pb(II) (0.08 μM) and Cd(II) (0.07 μM) as well as the superior linear relativity. In addition, an enhanced current at redox peaks, lower electron transfer resistance, larger BET surface area and stronger adsorption capacity have been confirmed for the balls NiO modified GCE surface. Finally, excellent stability and reproducibility of balls NiO modified electrodes for Pb(II) and Cd(II) detection have also been proved via the SWASV responses.

  5. 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

  6. 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.

  7. Improving lithium-sulphur batteries through spatial control of sulphur species deposition on a hybrid electrode surface.

    PubMed

    Yao, Hongbin; Zheng, Guangyuan; Hsu, Po-Chun; Kong, Desheng; Cha, Judy J; Li, Weiyang; Seh, Zhi Wei; McDowell, Matthew T; Yan, Kai; Liang, Zheng; Narasimhan, Vijay Kris; Cui, Yi

    2014-01-01

    Lithium-sulphur batteries are attractive owing to their high theoretical energy density and reasonable kinetics. Despite the success of trapping soluble polysulphides in a matrix with high surface area, spatial control of solid-state sulphur and lithium sulphide species deposition as a critical aspect has not been demonstrated. Herein, we show a clear visual evidence that these solid species deposit preferentially onto tin-doped indium oxide instead of carbon during electrochemical charge/discharge of soluble polysuphides. To incorporate this concept of spatial control into more practical battery electrodes, we further prepare carbon nanofibers with tin-doped indium oxide nanoparticles decorating the surface as hybrid three-dimensional electrodes to maximize the number of deposition sites. With 12.5 μl of 5 M Li2S8 as the catholyte and a rate of C/5, we can reach the theoretical limit of Li2S8 capacity ~\

  8. Surface-Controlled Mono/Diselective ortho C-H Bond Activation.

    PubMed

    Li, Qing; Yang, Biao; Lin, Haiping; Aghdassi, Nabi; Miao, Kangjian; Zhang, Junjie; Zhang, Haiming; Li, Youyong; Duhm, Steffen; Fan, Jian; Chi, Lifeng

    2016-03-01

    One of the most charming and challenging topics in organic chemistry is the selective C-H bond activation. The difficulty arises not only from the relatively large bond-dissociation enthalpy, but also from the poor reaction selectivity. In this work, Au(111) and Ag(111) surfaces were used to address ortho C-H functionalization and ortho-ortho couplings of phenol derivatives. More importantly, the competition between dehydrogenation and deoxygenation drove the diversity of reaction pathways of phenols on surfaces, that is, diselective ortho C-H bond activation on Au(111) surfaces and monoselective ortho C-H bond activation on Ag(111) surfaces. The mechanism of this unprecedented phenomenon was extensively explored by scanning tunneling microscopy, density function theory, and X-ray photoelectron spectroscopy. Our findings provide new pathways for surface-assisted organic synthesis via the mono/diselective C-H bond activation. PMID:26853936

  9. Excitation mechanism in the photoisomerization of a surface-bound azobenzene derivative: Role of the metallic substrate

    SciTech Connect

    Hagen, Sebastian; Kate, Peter; Leyssner, Felix; Nandi, Dhananjay; Wolf, Martin; Tegeder, Petra

    2008-10-28

    Two-photon photoemission spectroscopy is employed to elucidate the electronic structure and the excitation mechanism in the photoinduced isomerization of the molecular switch tetra-tert-butyl-azobenzene (TBA) adsorbed on Au(111). Our results demonstrate that the optical excitation and the mechanism of molecular switching at a metal surface is completely different compared to the corresponding process for the free molecule. In contrast to direct (intramolecular) excitation operative in the isomerization in the liquid phase, the conformational change in the surface-bound TBA is driven by a substrate-mediated charge transfer process. We find that photoexcitation above a threshold h{nu}{approx_equal}2.2 eV leads to hole formation in the Au d-band followed by a hole transfer to the highest occupied molecular orbital of TBA. This transiently formed positive ion resonance subsequently results in a conformational change. The photon energy dependent photoisomerization cross section exhibit an unusual shape for a photochemical reaction of an adsorbate on a metal surface. It shows a thresholdlike behavior below h{nu}{approx_equal}2.2 eV and above h{nu}{approx_equal}4.4 eV. These thresholds correspond to the minimum energy required to create single or multiple hot holes in the Au d-bands, respectively. This study provides important new insights into the use of light to control the structure and function of molecular switches in direct contact with metal electrodes.

  10. Adsorption of halide anions at the Pt(111)-solution interfacestudied by in situ surface x-ray scattering

    NASA Astrophysics Data System (ADS)

    Lucas, C. A.; Marković, N. M.; Ross, P. N.

    1997-03-01

    In this paper we present x-ray scattering results of iodide, bromide, and chloride adsorption onto the Pt(111) surface in solution. Iodide forms two commensurate adlayer structures, a (7×7)R19.1° phase and a hexagonal (3×3) phase, which coexist on the Pt surface. Formation of the (3×3) phase appears to be kinetically limited, whereas the 7 phase shows a hysteretic effect as a function of the electrode potential, associated with an order-disorder transition. Bromide forms a series of high-order commensurate structures on Pt(111) that are poorly ordered unless the size of the unit cell is small. No ordered structures for chloride adsorption are observed and specular x-ray reflectivity results suggest that the chloride coverage at low potential is too small to form a close-packed monolayer on the surface. The differences between the structures formed by the adsorbed anions, and the differences between results for Pt(111) and Au(111), are discussed in terms of the strength of the metal-halide interaction.

  11. Temperature distribution on anodic surface of membrane electrode assembly in proton exchange membrane fuel cell with interdigitated flow bed

    NASA Astrophysics Data System (ADS)

    Guo, Hang; Wang, Mao Hai; Liu, Jia Xing; Nie, Zhi Hua; Ye, Fang; Ma, Chong Fang

    2015-01-01

    Temperature distribution on the surface of a membrane electrode assembly (MEA) significantly influences the performance, lifetime, and reliability of proton exchange membrane fuel cells (PEMFCs). Entire temperature fields on the surface of an MEA anode side under an interdigitated flow field are experimentally measured at non-humidification conditions with a self-designed PEMFC and infrared imaging technology. The highest temperature on the surface of the MEA anode side appears in the bottom bordered two side channels, and the lowest temperature exists in the area closed to the inlet of the middle channel. The hot region on the surface of the MEA anode side is easy to locate in the infrared temperature image. The reason for the temperature distribution under the interdigitated flow field is analyzed. The temperature of the MEA, the non-uniformity of temperature distribution on the surface of the MEA anode side, and the fuel cell temperature increase with the loaded current density.

  12. 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).

  13. 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. PMID:26348658

  14. Surface-Supported Hydrocarbon π Radicals Show Kondo Behavior

    PubMed Central

    2013-01-01

    Stable hydrocarbon radicals are utilized as spin standards and prototype metal-free molecular magnets able to withstand ambient conditions. Our study presents experimental results obtained with submolecular resolution by scanning tunneling microscopy and spectroscopy from monomers and dimers of stable hydrocarbon π radicals adsorbed on the Au(111) surface at 7–50 K. We provide conclusive evidence of the preservation of the radical spin-1/2 state, aiming to establish α,γ-bisdiphenylene-β-phenylallyl (BDPA) on Au(111) as a novel Kondo system, where the impurity spin is localized in a metal-free π molecular orbital of a neutral radical state in gas phase preserved on a metal support. PMID:23539333

  15. An electrocorticographic electrode array for simultaneous recording from medial, lateral, and intrasulcal surface of the cortex in macaque monkeys

    PubMed Central

    Fukushima, Makoto; Saunders, Richard C.; Mullarkey, Matthew; Doyle, Alexandra M.; Mishkin, Mortimer; Fujii, Naotaka

    2014-01-01

    Background Electrocorticography (ECoG) permits recording electrical field potentials with high spatiotemporal resolution over a large part of the cerebral cortex. Application of chronically implanted ECoG arrays in animal models provides an opportunity to investigate global spatiotemporal neural patterns and functional connectivity systematically under various experimental conditions. Although ECoG is conventionally used to cover the gyral cortical surface, recent studies have shown the feasibility of intrasulcal ECoG recordings in macaque monkeys. New Method Here we developed a new ECoG array to record neural activity simultaneously from much of the medial and lateral cortical surface of a single hemisphere, together with the supratemporal plane (STP) of the lateral sulcus in macaque monkeys. The ECoG array consisted of 256 electrodes for bipolar recording at 128 sites. Results We successfully implanted the ECoG array in the left hemisphere of three rhesus monkeys. The electrodes in the auditory and visual cortex detected robust event related potentials to auditory and visual stimuli, respectively. Bipolar recording from adjacent electrode pairs effectively eliminated chewing artifacts evident in monopolar recording, demonstrating the advantage of using the ECoG array under conditions that generate significant movement artifacts. Comparison with Existing Methods Compared with bipolar ECoG arrays previously developed for macaque monkeys, this array significantly expands the number of cortical target areas in gyral and intralsulcal cortex. Conclusions This new ECoG array provides an opportunity to investigate global network interactions among gyral and intrasulcal cortical areas. PMID:24972186

  16. Evolution of Surface Motor Activation Zones in Hemiplegic Patients During 20 Sessions of FES Therapy with Multi-pad Electrodes.

    PubMed

    Malešević, Jovana; Štrbac, Matija; Isaković, Milica; Kojić, Vladimir; Konstantinović, Ljubica; Vidaković, Aleksandra; Dedijer, Suzana; Kostić, Miloš; Keller, Thierry

    2016-06-13

    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

  17. 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

  18. 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.

  19. 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.

  20. Calculating average surface enhancement factors of randomly nanostructured electrodes by a combination of SERS and impedance spectroscopy.

    PubMed

    Kozuch, J; Petrusch, N; Gkogkou, D; Gernert, U; Weidinger, I M

    2015-09-01

    Polyhedron Ag nanostructures were created on top of a polished Au electrode via step-wise electrodeposition and tested as substrates for SERS spectroscopy. Average Raman enhancement factors were derived by combining SERS measurements with electrochemical impedance spectroscopy (EIS), which is able to determine the electroactive surface area of a randomly nanostructured surface. Depending on the deposition step an alternating increase and decrease of surface area was observed while the SERS intensity showed a clear maximum for the first deposition cycle. SEM pictures reveal the formation of Ag polyhedrons that are randomly dispersed on the Au surface. Furthermore the presence of a sub nanostructure on top of the polyhedron after the first deposition cycle is observed which becomes smoother after subsequent deposition cycles. Correlating the SEM pictures with SERS and EIS measurements it is concluded that the coral-like sub nanostructure is dominating the enhancement factor while the polyhedron structure itself only plays a minor role for electromagnetic field enhancement. PMID:25599525

  1. 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

  2. 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

  3. Automated Targeting of Cells to Electrochemical Electrodes Using a Surface Chemistry Approach for the Measurement of Quantal Exocytosis

    PubMed Central

    2010-01-01

    Here, we describe a method to fabricate a multichannel high-throughput microchip device for the measurement of quantal transmitter release from individual cells. Instead of bringing carbon-fiber electrodes to cells, the device uses a surface chemistry approach to bring cells to an array of electrochemical microelectrodes. The microelectrodes are small and cytophilic in order to promote adhesion of a single cell, whereas all other areas of the chip are covered with a thin cytophobic film to block cell attachement and facilitate the movement of cells to electrodes. This cytophobic film also insulates unused areas of the conductive film; thus, the alignment of cell docking sites to working electrodes is automatic. Amperometric spikes resulting from single-granule fusion events were recorded on the device and had amplitudes and kinetics similar to those measured using carbon-fiber microelectrodes. Use of this device will increase the pace of basic neuroscience research and may also find applications in drug discovery or validation. PMID:21113333

  4. 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.

  5. 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

  6. 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

  7. Enhanced Output Power of PZT Nanogenerator by Controlling Surface Morphology of Electrode.

    PubMed

    Jung, Woo-Suk; Lee, Won-Hee; Ju, Byeong-Kwon; Yoon, Seok-Jin; Kang, Chong-Yun

    2015-11-01

    Piezoelectric power generation using Pb(Zr,Ti)O3(PZT) nanowires grown on Nb-doped SrTiO3(nb:STO) substrate has been demonstrated. The epitaxial PZT nanowires prepared by a hydrothermal method, with a diameter and length of approximately 300 nm and 7 μm, respecively, were vertically aligned on the substrate. An embossed Au top electrode was applied to maximize the effective power generation area for non-uniform PZT nanowires. The PZT nanogenerator produced output power density of 0.56 μW/cm2 with a voltage of 0.9 V and current of 75 nA. This research suggests that the morphology control of top electrode can be useful to improve the efficiency of piezoelectric power generation. PMID:26726616

  8. Spatially resolved electrochemistry in ionic liquids: surface structure effects on triiodide reduction at platinum electrodes.

    PubMed

    Aaronson, Barak D B; Lai, Stanley C S; Unwin, Patrick R

    2014-02-25

    Understanding the relationship between electrochemical activity and electrode structure is vital for improving the efficiency of dye-sensitized solar cells. Here, the reduction of triiodide to iodide in 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) room temperature ionic liquid (RTIL) is investigated on polycrystalline platinum using scanning electrochemical cell microscopy (SECCM) and correlated to the crystallographic orientation from electron backscatter diffraction (EBSD). Although the rate determining step in all grains was the first electron transfer, significant grain-dependent variations in activity were revealed, with grains with a dominant (110) crystallographic character exhibiting higher catalytic activity compared to those with a major (100) orientation. The SECCM technique is demonstrated to resolve heterogeneity in activity, highlighting that methods incorporating polycrystalline electrodes miss vital details for understanding and optimizing electrocatalysts. An additional advantage of the SECCM over single-crystal techniques is its ability to probe high index facets. PMID:24479903

  9. Electrochemical Behavior of Disposable Electrodes Prepared by Ion Beam Based Surface Modification for Biomolecular Recognition

    SciTech Connect

    Erdem, A.; Karadeniz, H.; Caliskan, A.; Urkac, E. Sokullu; Oztarhan, A.; Oks, E.; Nikolayev, A.

    2009-03-10

    Many important technological advances have been made in the development of technologies to monitor interactions and recognition events of biomolecules in solution and on solid substrates. The development of advanced biosensors could impact significantly the areas of genomics, proteomics, biomedical diagnostics and drug discovery. In the literature, there have recently appeared an impressive number of intensive designs for electrochemical monitoring of biomolecular recognition. Herein, the influence of ion implanted disposable graphite electrodes on biomolecular recognition and their electrochemical behaviour was investigated.

  10. 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.

  11. A simple and novel Si surface modification on LiFePO4@C electrode and its suppression of degradation of lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Yang, Wenyu; Zhuang, Zhenyuan; Chen, Xiang; Zou, Mingzhong; Zhao, Guiying; Feng, Qian; Li, Jiaxin; Lin, Yingbin; Huang, Zhigao

    2015-12-01

    A simple and novel surface modification device of the electrodes based on the ultrasonic spray technique was set up, which is considered to have the enormous prospect of industrial application due to its simpleness and high efficiency. Then, the nano-sized Si nanoparticles were deposited uniformly on the LiFePO4@C electrodes. In comparison with pristine LiFePO4@C electrode, the surface modification of the nano-sized Si with crystalline Si core and amorphous Si shell on the electrode surface exhibits less coarsening degree, higher rate capability, better cyclicity at high charge/discharge rate, especially at elevated temperature. Moreover, Raman spectra of LiFePO4@C, LiFePO4@C/Si electrodes before cycles and after 100 cycles at 1 C and 60 °C were measured. It is found that the FePO4 and α-Fe2O3 phases exist in LiFePO4@C after 100 cycles. On the contrary, there hardly exists the FePO4 and α-Fe2O3 phases, which means that the nano Si surface modification suppresses the degradation of lithium ion batteries. At last, the schematic and phenomenological resistance models of LiFePO4@C electrode modified by the nano-sized silicon particles have been suggested, which is responsible for the enhancement of the electrochemical performances after nano-sized Si surface modification.

  12. 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.

  13. 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.

  14. 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

  15. 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

  16. 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

  17. 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

  18. 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

  19. Oxidation of CO on a Pt-Fe alloy electrode studied by surface enhanced infrared reflection--absorption spectroscopy

    SciTech Connect

    Watanabe, Masahiro; Zhu, Yimin; Uchida, Hiroyuki

    2000-03-02

    To clarify the CO-tolerant mechanism at Pt-based alloy anode catalysts, surface-enhanced infrared reflection-absorption spectroscopy with the attenuated total reflection technique (ATR-SEIRAS), coupled with CV measurement, was used to observe the oxidation process of adsorbed CO on a typical Pt-Fe (Pt-Fe = 0.27/0.73) alloy. The alloy electrode exhibits a lower saturated coverage of CO ({theta}{sub co} = 0.55) than that of pure Pt ({theta}{sub co} = 1.0). The dominating linear CO is observed around 2,000 cm{sup {minus}1} when the equilibrium adlayer of CO covers the alloy electrode; however, linear and bridged CO and also COOH were found at the pure Pt electrode at the same CO coverage in the non-steady-state. On the basis of previous results that a Pt skin is formed during the repetitive potential cycling due to the dissolution of Fe on the alloy surface and the skin exhibits less electronic density in the d band, it can be explained that the lowered linear CO coverage and almost no bridged CO are obtained as the result of the lowered back-donation of d electrons from the Pt skin to adsorbates on the alloy surface. The wavenumber shift of the linear CO stretching to a lower value at the alloy, which is not simple predicted by the lowering of the back-donation of the electron, is ascribed to the weakening of the C -Pt bond. As a presumable effect of the electronic structure change at the Pt skin, the dissociation-oxidation of adsorbed water as well as a formation of adsorbed HOOH species are clearly observed beyond 0.6 V in the electrolyte solution without CO, which is different from that at the pure Pt electrode. Carbonate species can also be detected around 1,300--1,450 cm{sup {minus}1}, which are possibly produced by the surface reaction of CO{sub 2} with water.

  20. Polymeric ionic liquid and carbon black composite as a reusable supporting electrolyte: modification of the electrode surface.

    PubMed

    Yoo, Seung Joon; Li, Long-Ji; Zeng, Cheng-Chu; Little, R Daniel

    2015-03-16

    One of the major impediments to using electroorganic synthesis is the need for large amounts of a supporting electrolyte to ensure the passage of charge. Frequently this causes separation and waste problems. To address these issues, a polymeric ionic liquid-Super P carbon black composite has been formulated. The system enables electrolyses to be performed without adding an additional supporting electrolyte, and its efficient recovery and reuse. In addition, the ability of the composite to modify the electrode surface in situ leads to improved kinetics. A practical consequence is that one can decrease catalyst loading without sacrificing efficiency. PMID:25619992

  1. 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.

  2. 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

  3. Ullmann Reaction of Aryl Chlorides on Various Surfaces and the Application in Stepwise Growth of 2D Covalent Organic Frameworks.

    PubMed

    Shi, Ke Ji; Yuan, Ding Wang; Wang, Cheng Xin; Shu, Chen Hui; Li, Deng Yuan; Shi, Zi Liang; Wu, Xin Yan; Liu, Pei Nian

    2016-03-18

    On-surface Ullmann coupling reaction of aryl chlorides has been achieved on Cu(111), Ag(111), and Au(111), and the mechanism has been investigated on the single molecule level using scanning tunneling microscopy and density functional theory. The different reactivity of the aryl halides was utilized to design a stepwise on-surface synthesis, which affords a zigzag template and then converts to 2D porous networks. PMID:26938859

  4. 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

  5. Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode

    DOE PAGESBeta

    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

  6. 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

  7. 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

  8. 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.

  9. Microfabricated Surface-Electrode Ion Trap for Scalable Quantum Information Processing

    SciTech Connect

    Seidelin, S.; Chiaverini, J.; Reichle, R.; Bollinger, J.J.; Leibfried, D.; Britton, J.; Wesenberg, J.H.; Blakestad, R.B.; Epstein, R.J.; Hume, D.B.; Itano, W.M.; Jost, J.D.; Langer, C.; Ozeri, R.; Shiga, N.; Wineland, D.J.

    2006-06-30

    Individual laser-cooled {sup 24}Mg{sup +} ions are confined in a linear Paul trap with a novel geometry where gold electrodes are located in a single plane and the ions are trapped 40 {mu}m above this plane. The relatively simple trap design and fabrication procedure are important for large-scale quantum information processing (QIP) using ions. Measured ion motional frequencies are compared to simulations. Measurements of ion recooling after cooling is temporarily suspended yield a heating rate of approximately 5 motional quanta per millisecond for a trap frequency of 2.83 MHz, sufficiently low to be useful for QIP.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 1 μm-thickness ultra-flexible and high electrode-density surface electromyogram measurement sheet with 2 V organic transistors for prosthetic hand control.

    PubMed

    Fuketa, Hiroshi; Yoshioka, Kazuaki; Shinozuka, Yasuhiro; Ishida, Koichi; Yokota, Tomoyuki; Matsuhisa, Naoji; Inoue, Yusuke; Sekino, Masaki; Sekitani, Tsuyoshi; Takamiya, Makoto; Someya, Takao; Sakurai, Takayasu

    2014-12-01

    A 64-channel surface electromyogram (EMG) measurement sheet (SEMS) with 2 V organic transistors on a 1 μm-thick ultra-flexible polyethylene naphthalate (PEN) film is developed for prosthetic hand control. The surface EMG electrodes must satisfy the following three requirements; high mechanical flexibility, high electrode density and high signal integrity. To achieve high electrode density and high signal integrity, a distributed and shared amplifier (DSA) architecture is proposed, which enables an in-situ amplification of the myoelectric signal with a fourfold increase in EMG electrode density. In addition, a post-fabrication select-and-connect (SAC) method is proposed to cope with the large mismatch of organic transistors. The proposed SAC method reduces the area and the power overhead by 96% and 98.2%, respectively, compared with the use of conventional parallel transistors to reduce the transistor mismatch by a factor of 10. PMID:24951707

  15. Fuel cell electrodes

    DOEpatents

    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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. The Effects of TI/PT Bottom Electrode on Crystallographic and Surface Characteristics of PZT Thick Films

    NASA Astrophysics Data System (ADS)

    Koochekzadeh, Ali; Keshavarz Alamdari, Eskandar; Barzegar, Abdolghafar

    The ceramic lead zirconate titanate (PZT) films near the morphotropic phase boundary are successfully integrated into MEMS devices, especially for applications in microsensors and actuators. The ferro/piezo electric properties of PZT thick films are widely dependent on its surface quality and crystallographic orientation growth. This paper indicates the influences of platinum bottom electrode on the surface and crystallographic properties of PZT. Ti (10nm) and Pt (100nm) thin films have been deposited on silicon substrate by thermal evaporation and electron beam respectively without vacuum breaking. After annealing treatment, the Pt film exhibited (111) preferred orientation. Finally one micron thick PZT (54/46) film was deposited by a RF magnetron sputtering at room temperature in pure Argon followed by a conventional post annealing treatment on silicon substrate. The XRD measurements have shown the provskite structure of PZT films with (100) preferred orientation at annealing temperatures above 600°C and (111) preferred orientation above 650°c. The SEM results demonstrate that whatever the annealing temperature is increased, recrystallization grains and black holes on Pt surface occurs and cause morphological change of PZT surface. The AFM test shows the strong RMS roughness of platinum surface after annealing temperature at 650°C.

  3. Catalytic and Inhibitory Kinetic Behavior of Horseradish Peroxidase on the Electrode Surface

    PubMed Central

    Huang, Jitao; Huang, Wei; Wang, Titi

    2012-01-01

    Enzymatic biosensors are often used to detect trace levels of some specific substance. An alternative methodology is applied for enzymatic assays, in which the electrocatalytic kinetic behavior of enzymes is monitored by measuring the faradaic current for a variety of substrate and inhibitor concentrations. Here we examine a steady-state and pre-steady-state reduction of H2O2 on the horseradish peroxidase electrode. The results indicate the substrate-concentration dependence of the steady-state current strictly obeys Michaelis-Menten kinetics rules; in other cases there is ambiguity, whereby he inhibitor-concentration dependence of the steady-state current has a discontinuity under moderate concentration conditions. For pre-steady-state phases, both catalysis and inhibition show an abrupt change of the output current. These anomalous phenomena are universal and there might be an underlying biochemical or electrochemical rationale. PMID:23202175

  4. Nanocrystalline TiO{sub 2} (anatase) electrodes: Surface morphology, adsorption, and electrochemical properties

    SciTech Connect

    Kavan, L. |; Graetzel, M.; Rathousky, J.; Zukal, A.

    1996-02-01

    Films of sintered anatase nanoparticles are promising electrode materials for solar cells, electrochromics, and lithium batteries. For the last application, the anatase phase is essential, since the Li{sup +} insertion into other TiO{sub 2} polymorphs (rutile, brookite) is mostly considered to be negligible. Ten different nanotextured TiO{sub 2} films were prepared from six commercial and four laboratory synthesized precursors. Krypton adsorption isotherms on the films and apparent powders indicate the effect of sintering and agglomeration. Electrochemical characterization of the films was aimed at double-layer charging and Li{sup +} insertion. The relations between the film`s morphology, adsorption properties, and electrochemical behavior in the accumulation regime are discussed.

  5. Vapour-phase gold-surface-mediated coupling of aldehydes with methanol

    NASA Astrophysics Data System (ADS)

    Xu, Bingjun; Liu, Xiaoying; Haubrich, Jan; Friend, Cynthia M.

    2010-01-01

    Selective coupling of oxygenates is critical to many synthetic processes, including those necessary for the development of alternative fuels. We report a general process for selective coupling of aldehydes and methanol as a route to ester synthesis. All steps are mediated by oxygen-covered metallic gold nanoparticles on Au(111). Remarkably, cross-coupling of methanol with formaldehyde, acetaldehyde, benzaldehyde and benzeneacetaldehyde to methyl esters is promoted by oxygen-covered Au(111) below room temperature with high selectivity. The high selectivity is attributed to the ease of nucleophilic attack of the aldehydes by the methoxy intermediate-formed from methanol on the surface-which yields the methyl esters. The competing combustion occurs via attack of both methanol and the aldehydes by oxygen. The mechanistic model constructed in this study provides insight into factors that control selectivity and clearly elucidates the crucial role of Au nanoparticles as active species in the catalytic oxidation of alcohols, even in solution.

  6. New insights into the interface between a single-crystalline metal electrode and an extremely pure ionic liquid: slow interfacial processes and the influence of temperature on interfacial dynamics.

    PubMed

    Drüschler, Marcel; Borisenko, Natalia; Wallauer, Jens; Winter, Christian; Huber, Benedikt; Endres, Frank; Roling, Bernhard

    2012-04-21

    Ionic liquids are of high interest for the development of safe electrolytes in modern electrochemical cells, such as batteries, supercapacitors and dye-sensitised solar cells. However, electrochemical applications of ionic liquids are still hindered by the limited understanding of the interface between electrode materials and ionic liquids. In this article, we first review the state of the art in both experiment and theory. Then we illustrate some general trends by taking the interface between the extremely pure ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate and an Au(111) electrode as an example. For the study of this interface, electrochemical impedance spectroscopy was combined with in situ STM and in situ AFM techniques. In addition, we present new results for the temperature dependence of the interfacial capacitance and dynamics. Since the interfacial dynamics are characterised by different processes taking place on different time scales, the temperature dependence of the dynamics can only be reliably studied by recording and carefully analysing broadband capacitance spectra. Single-frequency experiments may lead to artefacts in the temperature dependence of the interfacial capacitance. We demonstrate that the fast capacitive process exhibits a Vogel-Fulcher-Tamman temperature dependence, since its time scale is governed by the ionic conductivity of the ionic liquid. In contrast, the slower capacitive process appears to be Arrhenius activated. This suggests that the time scale of this process is determined by a temperature-independent barrier, which may be related to structural reorganisations of the Au surface and/or to charge redistributions in the strongly bound innermost ion layer. PMID:22402629

  7. Analysis of solid electrolyte interface formation reaction and surface deposit of natural graphite negative electrode employing polyacrylic acid as a binder

    NASA Astrophysics Data System (ADS)

    Ui, Koichi; Fujii, Daisuke; Niwata, Yuki; Karouji, Tomohiro; Shibata, Yu; Kadoma, Yoshihiro; Shimada, Kazuaki; Kumagai, Naoaki

    2014-02-01

    We analyzed the solid electrolyte interface (SEI) formation reaction and surface deposit of a natural graphite (NG-3) electrode employing polyacrylic acid (PAA) as a binder in an ethylene carbonate-based electrolyte because it was reported that the initial charge-discharge characteristics of the NG-3 electrode were improved by employing the PAA binder. Poly(vinylidene fluoride) as a binder was used for comparison. We investigated the influence of the binder types on the coating of the NG-3 particles using the B.E.T. specific surface areas. The difference in the above phenomenon was explained by the relationship between the B.E.T. specific surface area and the irreversible capacity. The surface chemical composition of the NG-3 electrode was investigated by FE-SEM/EDX and XPS and then the difference between the PAA binder and the PVdF binder was discussed. The FE-SEM/EDX and the XPS results showed that the amount of the inorganic components of the SEI was relatively small in the case of the PAA binder NG-3 electrode. The AC impedance results showed that the SEI film resistance of the PAA binder NG-3 electrode was lower at 0.2 V. It was clarified that the binder types affected the coating state, the SEI formation reaction, and the SEI film composition.

  8. Ferrocene-1,1'-dithiol as molecular wire between Ag electrodes: The role of surface defects

    NASA Astrophysics Data System (ADS)

    Bredow, T.; Tegenkamp, C.; Pfnür, H.; Meyer, J.; Maslyuk, V. V.; Mertig, I.

    2008-02-01

    The interaction of ferrocene-1,1'-dithiol (FDT) with two parallel Ag(111) surfaces has been theoretically studied at density-functional level. The effect of surface defects on the energetic and electronic structure was investigated. The electronic transport properties are studied with the nonequilibrium Green's function approach. The adsorption geometry has a strong effect on the electronic levels and conductivity. The presence of point defects strongly enhances the molecule-surface interaction but has a surprisingly small effect on the density of states near the Fermi energy. The FDT-surface bond is particularly strong near terraces or steps and leads to significant shifts of the molecular orbitals relative to the gas phase. For all considered defect types except the single adatom the electronic conductivity through the FDT molecule is decreased compared to adsorption on perfect surfaces.

  9. Interrogation of surfaces for the quantification of adsorbed species on electrodes: oxygen on gold and platinum in neutral media.

    PubMed

    Rodríguez-López, Joaquín; Alpuche-Avilés, Mario A; Bard, Allen J

    2008-12-17

    We introduce a new in situ electrochemical technique based on the scanning electrochemical microscope (SECM) operating in a transient feedback mode for the detection and direct quantification of adsorbed species on the surface of electrodes. A SECM tip generates a titrant from a reversible redox mediator that reacts chemically with an electrogenerated or chemically adsorbed species at a substrate of about the same size as the tip, which is positioned at a short distance from it (ca.1 microm). The reaction between the titrant and the adsorbate provides a transient positive feedback loop until the adsorbate is consumed completely. The sensing mechanism is provided by the contrast between positive and negative feedback, which allows a direct quantification of the charge neutralized at the substrate. The proposed technique allows quantification of the adsorbed species generated at the substrate at a given potential under open circuit conditions, a feature not attainable with conventional electrochemical methods. Moreover, the feedback mode allows the tip to be both the titrant generator and detector, simplifying notably the experimental setup. The surface interrogation technique we introduce was tested for the quantification of electrogenerated oxides (adsorbed oxygen species) on gold and platinum electrodes at neutral pH in phosphate and TRIS buffers and with two different mediator systems. Good agreement is found with cyclic voltammetry at the substrate and with previous results in the literature, but we also find evidence for the formation of "incipient oxides" which are not revealed by conventional voltammetry. The mode of operation of the technique is supported by digital simulations, which show good agreement with the experimental results. PMID:19053403

  10. XPS investigation of surface reactivity of electrode materials: effect of the transition metal.

    PubMed

    Andreu, N; Flahaut, D; Dedryvère, R; Minvielle, M; Martinez, H; Gonbeau, D

    2015-04-01

    The role of the transition metal nature and Al2O3 coating on the surface reactivity of LiCoO2 and LiNi(1/3)Mn(1/3)Co(1/3)O2 (NMC) materials were studied by coupling chemisorption of gaseous probes molecules and X-ray photoelectron (XPS) spectroscopy. The XPS analyses have put in evidence the low reactivity of the LiMO2 materials toward basic gaseous probe (NH3). The reactivity toward SO2 gaseous probe is much larger (roughly more than 10 times) and strongly influenced by the nature of metal. Only one adsorption mode (redox process producing adsorbed sulfate species) was observed at the LiCoO2 surface, while NMC materials exhibit sulfate and sulfite species at the surface. On the basis of XPS analysis of bare materials and previous theoretical work, we propose that the acid-base adsorption mode involving the Ni(2+) cation is responsible for the sulfite species on the NMC surface. After Al2O3 coating, the surface reactivity was clearly decreasing for both LiCoO2 and NMC materials. In addition, for LiCoO2, the coating modifies the surface reactivity with the identification of both sulfate and sulfite species. This result is in line with a change in the adsorption mode from redox toward acid-base after Al/Co substitution. In the case of NMC materials, the coating induced a decrease of the sulfite species content at the surface. This phenomenon can be related to the cation mixing effect in the NMC. PMID:25751495

  11. Analysis of the Effect of Silicon with Nano-Size Surface Structure on an Electrode Formed Using Screen Printing.

    PubMed

    Kim, Min Young; Kim, Dae Sung; Byeon, Sung Kyun; Song, Woochang; Lim, Donggun

    2016-05-01

    In this paper, we report an investigation into the effects of the texturing size of silicon on the efficiency of a screen-printed Si solar cell. To accomplish this, we produced solar cells with various textured surfaces. The method we used to produce these cells included methods such as anisotropic chemical etching (texturing size of about 4 μm) using a mixed solution of KOH and IPA, reactive ion etching (texturing size of about 0.2 μm), and Ag catalyzed etching (texturing size of about 90 nm). The solar cells with an Ag-catalyzed etching textured structure showed the lowest efficiency of 11.87%, with the highest series resistance of 1.32 Ω. In the case of anisotropic chemical etching, the solar cell had the best efficiency of 17.84%, with the lowest series resistance. This means that the electrodes and silicon surfaces were not well-connected with the nano-sized textured silicon surface. The results revealed that conventional silver paste at an average of 1.6 μm is unsuitable for nano-sized textured Si solar cells. PMID:27483903

  12. Hierarchical Porous and High Surface Area Tubular Carbon as Dye Adsorbent and Capacitor Electrode.

    PubMed

    Chen, Long; Ji, Tuo; Brisbin, Logan; Zhu, Jiahua

    2015-06-10

    Hierarchically porous tubular carbon (HPTC) with large surface area of 1094 m(2)/g has been successfully synthesized by selectively removing lignin from natural wood. No templates or chemicals are involved during the process. By further KOH activation, surface area of activated HPTC reaches up to 2925 m(2)/g. These materials show unprecedented high adsorption capacity toward organic dyes (methylene blue, 838 mg/g; methyl orange, 264 mg/g) and large electrochemical capacitance of >200 F/g. The sustainable feature of the wood precursor and demonstrated superior adsorption and energy storage properties allow promising applications of the processed materials in energy and environmental related fields. PMID:25980528

  13. 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

  14. 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

  15. 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

  16. 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. PMID:25557533

  17. 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

  18. Design and evaluation of a highly sensitive nanostructure-based surface modification of glassy carbon electrode for electrochemical studies of hydroxychloroquine in the presence of acetaminophen.

    PubMed

    Khoobi, Asma; Ghoreishi, Sayed Mehdi; Behpour, Mohsen; Shaterian, Maryam; Salavati-Niasari, Masoud

    2014-11-01

    N,N'-bis[(E)-(1-pyridyl) methylidene]-1,3-propanediamine (PMPDA) self-assembled monolayer (SAM) was covalently prepared on a glassy carbon electrode (GCE). The electrode surface modification was characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques. Then GC-PMPDA SAM modified electrode was used to investigate the electrochemical behavior of hydroxychloroquine (HQ) using CV, double potential step chronocoulometry and linear sweep voltammetry (LSV) techniques. Using these techniques, the diffusion coefficient (D), electron transfer coefficient (α) and exchanging current density (j0) for HQ were calculated. Furthermore the modified electrode was applied as a high sensitive biosensor for determination of HQ in the presence of acetaminophen (AC). The GC-PMPDA SAM modified electrode provides two linear responses for HQ in the presence of AC in the concentration ranges from 0.09 to 10.21 μM and 10.21 to 98.29 μM by differential pulse voltammetry (DPV). The detection limit (three times the signal blank/slope) was 4.65 nM. Finally the modified electrode was satisfactorily used for determining of HQ in human body fluids. PMID:25456984

  19. Shattering of SiMe3+ during surface-induced dissociation

    NASA Astrophysics Data System (ADS)

    Schultz, David G.; Hanley, Luke

    1998-12-01

    We provide experimental evidence that upon hyperthermal impact of Si(CD3)3+ ions with an organic surface, a portion of the ions undergo dissociation while still in contact with the surface. We use a tandem configuration of quadrupole mass spectrometers along with an energy analyzer to measure the kinetic energy distributions of the fragments that form as a result of the surface scattering of 25 eV Si(CD3)3+. These distributions are different for scattering from a clean Au(111) surface versus scattering from an organic surface composed of a self-assembled monolayer of hexanethiolate on Au(111). Parent and fragment ions recoil from the clean Au(111) surface with the same velocity, as is expected for fragmentation away from the surface. However, the same scattering products recoil from the organic surface with different velocities but similar energies, suggesting that the fragmentation dynamics are modified by surface interactions. We perform molecular dynamics simulations which predict residence times of ˜210 fs at the organic surface and ˜20 fs at the Au surface. The simulations also predict that 13% and 31% of the ions fragment within 1.1 ps of surface impact at the organic and Au surfaces, respectively. Thus, the experimental observation of dissociation at only the organic surface results from its longer ion-surface interaction time. The fragmentation time scale predicted by Rice-Ramsperger-Kassel-Marcus calculations is yet longer, suggesting that at least a portion of the surface-induced dissociation of Si(CD3)3+ may occur via a nonstatistical mechanism. Our interpretation draws heavily from an analogous "shattering" mechanism previously proposed for cluster-surface scattering [E. Hendell, U. Even, T. Raz, and R. D. Levine, Phys. Rev. Lett. 75, 2670 (1995)].

  20. Electrode surface modification for cathode catalysis in semi-fuel cells. End of the year report

    SciTech Connect

    Bessette, R.R.

    1998-07-07

    The program objective is to identify the optimum conditions for fabricating a stable electrocatalytic cathode of palladium and iridium that will: improve the cathode polarization potential, diminish the heterogeneous decomposition and direct chemical reactions and significantly improve (gain of 50%) the overall electrochemical cell efficiency. The second objective is to evaluate the electrochemical performance of the catalyzed cathode. The third objective is to characterize the structure and composition of the catalytic surface.

  1. 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.

  2. Quantitative SHINERS analysis of temporal changes in the passive layer at a gold electrode surface in a thiosulfate solution.

    PubMed

    Smith, Scott R; Leitch, J Jay; Zhou, Chunqing; Mirza, Jeff; Li, Song-Bo; Tian, Xiang-Dong; Huang, Yi-Fan; Tian, Zhong-Qun; Baron, Janet Y; Choi, Yeonuk; Lipkowski, Jacek

    2015-04-01

    Shell-isolated gold nanoparticles (SHINs) were employed to record shell-isolated nanoparticle-enhanced Raman spectra (SHINERS) of a passive layer formed at a gold surface during gold leaching from thiosulfate solutions. The (3-aminopropyl)triethoxysilane (APTES) and a sodium silicate solution were used to coat gold nanoparticles with a protective silica layer. This protective silica layer prevented interactions between the thiosulfate electrolyte and the gold core of the SHINs when the SHINs-modified gold electrode was immersed into the thiosulfate lixiviant. The SHINERS spectra of the passive layer, formed from thiosulfate decomposition, contained bands indicative of hydrolyzed APTES. We have demonstrated how to exploit the presence of these APTES bands as an internal standard to compensate for fluctuations of the surface enhancement of the electric field of the photon. We have also developed a procedure that allows for removal of the interfering APTES bands from the SHINERS spectra. These methodological advancements have enabled us to identify the species forming the passive layer and to determine that the formation of elemental sulfur, cyclo-S8, and polymeric sulfur chains is responsible for inhibition of gold dissolution in oxygen rich thiosulfate solutions. PMID:25751526

  3. 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.

  4. 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.

  5. Surface-enhanced Raman scattering and atomic force microscopy of brass electrodes in sulfuric acid solution containing benzotriazole and chloride ion

    SciTech Connect

    Rubim, J.C.; Kim, J.; Henderson, E.; Cotton, T.M. Ames Lab., IA Iowa State Univ., Ames )

    1993-01-01

    Three different methods were used to roughen brass (Cu/Zn = 67/33) electrodes in 0.5 M H[sub 2]SO[sub 4] containing 1.0 mM benzotriazole (BTAH): (1) polarization at +0.05 V vs. saturated calomel for 5 min; (2) immersion in the above solution for six hours; and (3) oxidation-reduction cycling in the presence of chloride ion. The surfaces prepared by the first two methods exhibited surface-enhanced Raman scattering (SERS) spectra of the polymeric complex [Cu(I)BTA][sub s]. The SERS spectrum obtained from electrodes prepared by the third method is very similar to that of [Cu(I)CIBTAH][sub 4]. Examination of the electrodes by atomic force microscopy (AFM) showed that a large number of grain boundary sites are formed by the roughening processes. This effect is attributed to the loss of zinc, which occurs during corrosion of the mirror-like, polished brass electrode surface in the sulfuric acid solution. 11 refs., 5 figs.

  6. Smooth electrode and method of fabricating same

    SciTech Connect

    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.

  7. 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.

  8. Concentration and density changes at an electrode surface and the principle of unchanging total concentration

    DOE PAGESBeta

    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

  9. Optimal spacing of surface electrode arrays for brain-machine interface applications

    NASA Astrophysics Data System (ADS)

    Slutzky, Marc W.; Jordan, Luke R.; Krieg, Todd; Chen, Ming; Mogul, David J.; Miller, Lee E.

    2010-04-01

    Brain-machine interfaces (BMIs) use signals recorded directly from the brain to control an external device, such as a computer cursor or a prosthetic limb. These control signals have been recorded from different levels of the brain, from field potentials at the scalp or cortical surface to single neuron action potentials. At present, the more invasive recordings have better signal quality, but also lower stability over time. Recently, subdural field potentials have been proposed as a stable, good quality source of control signals, with the potential for higher spatial and temporal bandwidth than EEG. Here we used finite element modeling in rats and humans and spatial spectral analysis in rats to compare the spatial resolution of signals recorded epidurally (outside the dura), with those recorded from subdural and scalp locations. Resolution of epidural and subdural signals was very similar in rats and somewhat less so in human models. Both were substantially better than signals recorded at the scalp. Resolution of epidural and subdural signals in humans was much more similar when the cerebrospinal fluid layer thickness was reduced. This suggests that the less invasive epidural recordings may yield signals of similar quality to subdural recordings, and hence may be more attractive as a source of control signals for BMIs.

  10. Space and surface charge excitation of a slanted dielectric interface between two electrodes

    SciTech Connect

    Seidel, D.B.; Levinson, C.L.

    1982-09-01

    The two-dimensional, electrostatic problem of a planar dielectric interface between two perfectly conducting plates has been solved numerically. The solution allows for an arbitrary interface angle relative to the plates as well as arbitrary distributions of both charge within the volume and surface charge along the interface. The problem is treated by first converting the governing differential equations to a pair of coupled integral equations using Green's function techniques, then solving these integral equations numerically using moment methods. This report details this solution and shows some sample results. This work was motivated by the need to understand the physics of dielectric breakdown by flashover in high voltage insulator applications. Of particular interest is the physics associated with Magnetic Flashover Inhibition (MFI), a possible method of significantly increasing insulator breakdown strength above that possible using currently proven technologies. A solution of this type has several apparent advantages over existing techniques for treating this type of problem and is currently being adapted for use in an existing two-dimensional Particle-In-Cell (PIC) code.

  11. 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.

  12. Spin transport properties of n-polyacene molecules (n = 1–15) connected to Ni surface electrodes: Theoretical analysis

    PubMed Central

    Caliskan, S.; Laref, A.

    2014-01-01

    Using non-equilibrium Green function formalism in conjunction with density functional theory, we explore the spin-polarized transport characteristics of several planar n-acene molecules suspended between two semi-infinite Ni electrodes via the thiol group. We examine the spin-dependence transport on Ni-n-acenes-Ni junctions, while the number of fused benzene rings varies between 1 and 15. Intriguingly, the induced magnetic moments of small acene molecules are higher than that of longer acene rings. The augmentation of fused benzene rings affects both the magnetic and transport features, such as the transmission function and conductance owing to their coupling to the Ni surface contacts via the anchoring group. The interplay between the spin-polarized transport properties, structural configuration and molecular electronic is a fortiori essential in these attractive molecular devices. Thus, this can conduct to the engineering of the electron spin transport in atomistic and molecular junctions. These prominent molecules convincingly infer that the molecular spin valves can conduct to thriving molecular devices. PMID:25482076

  13. Control of work function of indium tin oxide: A surface treatment by atmospheric-pressure plasma layer on fabric-type electrodes

    NASA Astrophysics Data System (ADS)

    Ueda, Yoshihiko; Abe, Junichi; Murata, Hideyuki; Gotoh, Yasuhito; Sakai, Osamu

    2014-01-01

    The surface electronic properties of metal oxides, which affect the performances of layered electronic devices, are controlled by non-thermal atmospheric-pressure plasmas generated using a fabric-type electrode and gas flow induced through this plasma layer. We specify a method to control the work function of indium tin oxide (ITO) films by this plasma, in which such reactive species as oxidant radicals are generated. These oxidants are spatially transported in the gas flow to the ITO surface and increase the ITO’s work function, as verified in our experimental results. To examine the effects of the increased work function in a specific electronic device, we treat the surface of an ITO electrode in an organic light-emitting diode and observe the enhancement of the light-emitting efficiency.

  14. 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.

  15. 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.

  16. Disposable biomedical electrode

    NASA Technical Reports Server (NTRS)

    Frost, J. D., Jr.; Hillman, C. E., Jr.

    1977-01-01

    Reusable recording cap equipped with compressible snap-on bioelectronic electrodes is worn by patient to allow remote monitoring of electroencephalogram and electro-oculogram waveforms. Electrodes can be attached to inside surface of stretch-textile cap at twelve monitoring positions and at one or two ground positions.

  17. Structural Variation in Surface-Supported Synthesis by Adjusting the Stoichiometric Ratio of the Reactants.

    PubMed

    Gong, Zhongmiao; Yang, Biao; Lin, Haiping; Tang, Yunyu; Tang, Zeyuan; Zhang, Junjie; Zhang, Haiming; Li, Youyong; Xie, Yongshu; Li, Qing; Chi, Lifeng

    2016-04-26

    Surface-supported coupling reactions between 1,3,5-tris(4-formylphenyl)benzene and aromatic amines have been investigated on Au(111) using scanning tunneling microscopy under ultra-high-vacuum conditions. Upon annealing to moderate temperatures, various products, involving the discrete oligomers and the surface covalent organic frameworks, are obtained through thermal-triggered on-surface chemical reactions. We conclude from the systematic experiments that the stoichiometric composition of the reactants is vital to the surface reaction products, which is rarely reported so far. With this knowledge, we have successfully prepared two-dimensional covalently bonded networks by optimizing the stoichiometric proportions of the reaction precursors. PMID:27043277

  18. Electroretinographic wet electrode.

    PubMed

    Carpi, Federico; Benini, Gabriella; Tomei, Franca; Figliuzzi, Rosa Maria; De Napoli, Alberto

    2009-10-01

    This paper presents the first systematic characterisation of a new electroretinographic (ERG) electrode, recently described. The new 'wet' electrode uses a conducting liquid as a distributed electrical interface between the eye and a solid electronic conductor; the latter detects the ERG potential without any direct contact with the ocular surface. This technique avoids the contact-induced discomfort of both corneal and conjunctival standard electrodes. The wet electrode was tested on 10 volunteers, in comparison with a conjunctival electrode (HK loop), as the most comfortable standard. It was also compared with a cutaneous (cup) electrode, which is even more comfortable, although not standard. Results showed the efficacy of the wet electrode for detecting morphologically accurate ERG responses, with amplitudes respectively analogous and higher of those measured by the conjunctival and cutaneous electrodes. Properties of wet electrodes include: no solid interface with the eye, no need for anaesthesia, intrinsic safety, mechanical and electrical stability against ocular movements, tolerance to misplacements and immunity to lacrimation. As a drawback, the liquid can still be a source of discomfort for some patients and it requires care against possible leakage. All these features suggest a possible use of wet electrodes as an additional tool for ERG procedures, although limited to tests of short duration. PMID:19501539

  19. Electrochemical driven water oxidation by molecular catalysts in situ polymerized on the surface of graphite carbon electrode.

    PubMed

    Wang, Lei; Fan, Ke; Daniel, Quentin; Duan, Lele; Li, Fusheng; Philippe, Bertrand; Rensmo, Håkan; Chen, Hong; Sun, Junliang; Sun, Licheng

    2015-05-01

    A simple strategy to immobilize highly efficient ruthenium based molecular water-oxidation catalysts on the basal-plane pyrolytic graphite electrode (BPG) by polymerization has been demonstrated. The electrode 1@BPG has obtained a high initial turnover frequency (TOF) of 10.47 s(-1) at ∼700 mV overpotential, and a high turnover number (TON) up to 31600 in 1 h electrolysis. PMID:25854858

  20. Shape and size control of Cu nanoparticles by tailoring the surface morphologies of TiN-coated electrodes for biosensing applications.

    PubMed

    Yang, Chia-Jung; Lu, Fu-Hsing

    2013-12-23

    A method for controlling the shapes and sizes of Cu nanoparticles during electrodeposition has been developed by tailoring the surface morphologies of TiN-coated electrodes. Larger octahedral Cu NPs grew on a granular TiN film; smaller, irregular Cu NPs formed on a pyramidal TiN film. The surface morphology of the TiN film affected the accumulation of Cu(2+) and hexadecyltrimethylammonium (CTA(+)) ions, leading to the different shapes and sizes of the resulting Cu NPs. The significant steric effect of the CTA(+) ions was confirmed when using the film of pyramidal TiN as the electrode in the CTAB-containing electrolyte; it contributed to the growth of the smaller, irregular Cu NPs. The sensitivity of the smaller, irregular Cu NPs in the detection of glucose was better than that of the larger, octahedral Cu NPs because of the former's greater increase in the Cu(2+)-to-Cu(0) ratio. PMID:24320707