Potential-induced structural transitions of DL-homocysteine monolayers on Au(111) electrode surfaces

DEFF Research Database (Denmark)

Zhang, Jingdong; Demetriou, Anna; Welinder, Anne Christina

2005-01-01

Monolayers of homocysteine on Au(111)-surfaces have been investigated by voltammetry, in situ scanning tunnelling microscopy (STM) and subtractively normalised interfacial Fourier transform spectroscopy (SNIFTIRS). A pair of sharp voltammetric peaks build up in the potential range 0 to -0.1 V (vs...... potentials at pH 7.7. The molecules pack into highly ordered domains around the peak potential. High-resolution in situ STM reveals a (root 3 x 5) R30 degrees lattice with three homocysteine molecules in each unit cell. The adlayer changes into disordered structures on either side of the peak potential...

Carbon monoxide oxidation on a Au(111 surface modified by spontaneously deposited Ru

Directory of Open Access Journals (Sweden)

ROLF-JÜRGEN BEHM

2001-04-01

Full Text Available The spontaneous deposition of Ru on Au(111 was performed in 10-3 M RuCl3 + 0.5 M H2SO4 solution. The obtained surface was characterized by STM under potential control in 0.5 M H2SO4 solution. The coverage of the Au(111 terraces by deposited Ru was estimated by STM to be 0.02 ML. Step decoration could be noticed in the STM images, which indicates that the steps, as lined defects, are active sites for the nucleation of Ru monolayer islands, while the random distribution of Ru nuclei, observed on the terraces indicates point defects as active sites. The electrocatalytic activity of Au(111 surface modified by spontaneously deposited Ru was studied towards CO oxidation. The significant enhancement in the reaction rate compared to CO oxidation on a pure Au(111 surface, indicated that the edges of the deposited Ru islands were the active sites for the reaction.

Potential-induced structural transitions of DL-homocysteine monolayers on Au(111) electrode surfaces

International Nuclear Information System (INIS)

Zhang Jingdong; Demetriou, Anna; Welinder, Anne Christina; Albrecht, Tim; Nichols, Richard J.; Ulstrup, Jens

2005-01-01

Monolayers of homocysteine on Au(111)-surfaces have been investigated by voltammetry, in situ scanning tunnelling microscopy (STM) and subtractively normalised interfacial Fourier transform spectroscopy (SNIFTIRS). A pair of sharp voltammetric peaks build up in the potential range 0 to -0.1V (vs. SCE) in phosphate buffer pH 7.7. The peak half-widths are about 25mV at a scan rate of 10mVs -1 . This is much smaller than for a one-electron Faradaic process (90.6mV) under similar conditions. The coverage of homocysteine is 6.1 (+/-0.2)x10 -10 molcm -2 , or 5.9x10 -5 Ccm -2 , from Au-S reductive desorption at -0.8V (SCE) in 0.1M NaOH, while the charge is only about 8x10 -6 Ccm -2 (pH 7.7) for the 0 to -0.1V peak. This suggests a capacitive origin. The peak potential and shape depend on pH. At pH 7.7 both cathodic and anodic peak currents reach a maximum, but drop at both higher and lower pH. The midpoint potential shows biphasic behaviour, decreasing linearly with increasing pH until pH 10.4 towards a constant value at higher pH. The cathodic and anodic peak charges decay at pH both higher and lower than 7.7. The homocysteine monolayer was investigated by in situ STM at different potentials at pH 7.7. The molecules pack into highly ordered domains around the peak potential. High-resolution in situ STM reveals a (√3x5) R30 deg. lattice with three homocysteine molecules in each unit cell. The adlayer changes into disordered structures on either side of the peak potential. This process is reversible. We propose that the voltammetric peaks are capacitive. The ordered domains are formed only around the potential of zero charge (pzc) and dissipate at potentials on either side of the peak, inducing mirror charge flow in the metallic electrode as the charged -COO - and -NH 3 + groups approach the surface. No bands for carboxylate coordinated to the surface were observed in SNIFTIRS implying more subtle orientation changes of the charged groups on transcending the voltammetric

Self-organization of a self-assembled supramolecular rectangle, square, and three-dimensional cage on Au111 surfaces.

Science.gov (United States)

Yuan, Qun-Hui; Wan, Li-Jun; Jude, Hershel; Stang, Peter J

2005-11-23

The structure and conformation of three self-assembled supramolecular species, a rectangle, a square, and a three-dimensional cage, on Au111 surfaces were investigated by scanning tunneling microscopy. These supramolecular assemblies adsorb on Au111 surfaces and self-organize to form highly ordered adlayers with distinct conformations that are consistent with their chemical structures. The faces of the supramolecular rectangle and square lie flat on the surface, preserving their rectangle and square conformations, respectively. The three-dimensional cage also forms well-ordered adlayers on the gold surface, forming regular molecular rows of assemblies. When the rectangle and cage were mixed together, the assemblies separated into individual domains, and no mixed adlayers were observed. These results provide direct evidence of the noncrystalline solid-state structures of these assemblies and information about how they self-organize on Au111 surfaces, which is of importance in the potential manufacturing of functional nanostructures and devices.

Hydrogen evolution on Au(111) covered with submonolayers of Pd

DEFF Research Database (Denmark)

Björketun, Mårten; Karlberg, Gustav; Rossmeisl, Jan

2011-01-01

A theoretical investigation of electrochemical hydrogen evolution on Au(111) covered with submonolayers of Pd is presented. The size and shape of monoatomically high Pd islands formed on the Au(111) surface are determined using Monte Carlo simulations, for Pd coverages varying from 0.02 to 0.95 ML....... The energetics of adsorption and desorption of hydrogen on/from different types of sites on the Pd-Au(111) surface are assessed by means of density functional theory calculations combined with thermodynamic modeling. Based on the density functional and Monte Carlo data, the hydrogen evolution activity...... is evaluated with a micro-kinetic model. The analysis reproduces measured Pd-coverage-dependent activities for Pd submonolayers exceeding similar to 0.15 ML and enables the relative contributions from different types of electrocatalytically active sites to be determined. Finally, the implications of surface...

A first principles study on the electronic origins of silver segregation at the Ag-Au (111) surface

Science.gov (United States)

Hoppe, Sandra; Müller, Stefan

2017-12-01

The special electronic structure of gold gives rise to many interesting phenomena, such as its color. The surface segregation of the silver-gold system has been the subject of numerous experimental and theoretical studies, yielding conflicting results ranging from strong Ag surface enrichment to Au surface segregation. Via a combined approach of density functional theory (DFT) and statistical physics, we have analyzed the segregation at the Ag-Au (111) surface with different Ag bulk concentrations. Interestingly, we observe a moderate Au surface segregation, which is due to a charge transfer from the less electronegative Ag to Au. Canonical Monte Carlo simulations suggest that the calculated concentration profile with a Au-enriched surface layer remains stable up to higher temperatures. However, the presence of adsorbed oxygen reverses the segregation behavior and leads to strong Ag enrichment of the surface layer.

Energy-resolved attosecond interferometric photoemission from Ag(111) and Au(111) surfaces

Science.gov (United States)

Ambrosio, M. J.; Thumm, U.

2018-04-01

Photoelectron emission from solid surfaces induced by attosecond pulse trains into the electric field of delayed phase-coherent infrared (IR) pulses allows the surface-specific observation of energy-resolved electronic phase accumulations and photoemission delays. We quantum-mechanically modeled interferometric photoemission spectra from the (111) surfaces of Au and Ag, including background contributions from secondary electrons and direct emission by the IR pulse, and adjusted parameters of our model to energy-resolved photoelectron spectra recently measured at a synchrotron light source by Roth et al. [J. Electron Spectrosc. 224, 84 (2018), 10.1016/j.elspec.2017.05.008]. Our calculated spectra and photoelectron phase shifts are in fair agreement with the experimental data of Locher et al. [Optica 2, 405 (2015), 10.1364/OPTICA.2.000405]. Our model's not reproducing the measured energy-dependent oscillations of the Ag(111) photoemission phases may be interpreted as evidence for subtle band-structure effects on the final-state photoelectron-surface interaction not accounted for in our simulation.

Structure investigation of organic molecules on Au(111) surfaces; Strukturuntersuchung organischer Molekuele auf Au(111)-Oberflaechen

Energy Technology Data Exchange (ETDEWEB)

Kazempoor, Michel

2009-02-02

The present work covers two topics namely the coadsorption of formic acid and water on Au(111) and the structure of biphenylalkanthiole SAMs on Au(111) surfaces. The coadsorption of formic acid and water on Au(111) surfaces has been investigated by means of vibrational and photoelectron spectroscopy (HREELS, XPS). Formic acid adsorbs at 90 K molecularly with vibrational modes characteristic for flat lying zig-zag chains in the mono- and multilayer regime, like in solid formic acid. The structure of the flat lying formic acid chains was determined by low energy electron diffraction (LEED) as a (2r3 x r19) unit cell. Annealing results in a complete desorption at 190 K. Sequential adsorption of formic acid and water at 90 K shows no significant chemical interaction. Upon annealing the coadsorbed layer to 140 K a hydrogenbonded cyclic complex of formic acid with one water molecule could be identified using isotopically labelled adsorbates. Upon further annealing this complex decomposes leaving molecularly adsorbed formic acid on the surface at 160 K, accompanied by a proton exchange between formic acid and water. The influence of the alkane spacer chain length on the structure of biphenylalkanethiols on Au(111) surfaces was investigated as well. A systematic study was done on BPn-SAMs deposited from the gas phase. For every chain length a structure was found by LEED. Furthermore the influence of temperature on the structure was investigated in the range from room temperature up to about 400 K. To obviate influences from different preparation methods BP3 and BP4 was deposited from gas phase and from solution. No LEED spots were observed on BP4 SAMs deposited from solution. For BP3 an influence of the preparation could be excluded. For all BPn-SAMs a good agreement between LEED and STM data's was found. Nevertheless different unit cells were determined by LEED and STM consistent structures could be suggested considering the unit cell size given by LEED and the

Mapping the Diffusion Potential of a Reconstructed Au(111) Surface at Nanometer Scale with 2D Molecular Gas

International Nuclear Information System (INIS)

Yan Shi-Chao; Xie Nan; Gong Hui-Qi; Guo Yang; Shan Xin-Yan; Lu Xing-Hua; Sun Qian

2012-01-01

The adsorption and diffusion behaviors of benzene molecules on an Au(111) surface are investigated by low-temperature scanning tunneling microscopy. A herringbone surface reconstruction of the Au(111) surface is imaged with atomic resolution, and significantly different behaviors are observed for benzene molecules adsorbed on step edges and terraces. The electric field induced modification in the molecular diffusion potential is revealed with a 2D molecular gas model, and a new method is developed to map the diffusion potential over the reconstructed Au(111) surface at the nanometer scale. (condensed matter: structure, mechanical and thermal properties)

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

International Nuclear Information System (INIS)

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

2009-01-01

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.

In situ STM imaging and direct electrochemistry of Pyrococcus furiosus ferredoxin assembled on thiolate-modified Au(111) surfaces

DEFF Research Database (Denmark)

Zhang, Jingdong; Christensen, Hans Erik Mølager; Ooi, Bee Lean

2004-01-01

We have addressed here electron transfer (ET) of Pyrococcus furiosus ferredoxin (PfFd, 7.5 kDa) in both homogeneous solution using edge plane graphite (EPG) electrodes and in the adsorbed state by electrochemistry on surface-modified single-crystal Au(111) electrodes, This has been supported...... by surface microscopic structures of PfFd monolayers, as revealed by scanning tunneling microscopy under potential control (in situ STM). Direct ET between PfFd in phosphate buffer solution, pH 7.9, and EPG electrodes is observed in the presence of promoters. Neomycin gives rise to a pair of redox peaks...... with a formal potential of ca -430 mV (vs SCE), corresponding to [3Fe-4S](1+/0). The presence of an additional promoter, which can be propionic acid, alanine, or cysteine, induces a second pair of redox peaks at similar to-900 mV (vs SCE) arising from [3Fe-4S](0/1-). A robust neomycin-PfFd complex was detected...

RPBE-vdW Description of Benzene Adsorption on Au(111)

DEFF Research Database (Denmark)

Pedersen, Jess Wellendorff; Kelkkanen, Kari André; Mortensen, Jens Jørgen

2010-01-01

Density functional theory has become a popular methodology for the analysis of molecular adsorption on surfaces. Despite this popularity, there exist adsorption systems for which commonly used exchange-correlation functionals fail miserably. Particularly those systems where binding is due to van...... der Waals interactions. The adsorption of benzene on Au(111) is an often mentioned such system where standard density functionals predict a very weak adsorption or even a repulsion, whereas a significant adsorption is observed experimentally. We show that a considerable improvement in the description...... of the adsorption of benzene on Au(111) is obtained when using the so-called RPBE-vdW functional....

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

Science.gov (United States)

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.

Overlayer structure of subphthalocyanine derivative deposited on Au (111) surface by a spray-jet technique

International Nuclear Information System (INIS)

Suzuki, Hitoshi; Yamada, Toshiki; Miki, Hideki; Mashiko, Shinro

2006-01-01

A new spray-jet technique was used to deposit subphthalocyanine derivative (chloro[tri-tert-butyl subphthalocyaninato]boron (TBSubPc)) on Au (111) surface in an ultra-high vacuum (UHV) chamber. The deposited molecular overlayer was observed with UHV scanning tunneling microscopy (STM) at 77 K. The STM images showed that TBSubPc molecules formed a stripe pattern with regular spacing, indicating that they preferentially adsorbed along the herringbone structure of the Au (111) surface. This behavior was very similar to that of TBSubPc molecules deposited by thermal evaporation

Quantum tunneling in real space: Tautomerization of single porphycene molecules on the (111) surface of Cu, Ag, and Au

Science.gov (United States)

Kumagai, Takashi; Ladenthin, Janina N.; Litman, Yair; Rossi, Mariana; Grill, Leonhard; Gawinkowski, Sylwester; Waluk, Jacek; Persson, Mats

2018-03-01

Tautomerization in single porphycene molecules is investigated on Cu(111), Ag(111), and Au(111) surfaces by a combination of low-temperature scanning tunneling microscopy (STM) experiments and density functional theory (DFT) calculations. It is revealed that the trans configuration is the thermodynamically stable form of porphycene on Cu(111) and Ag(111), whereas the cis configuration occurs as a meta-stable form. The trans → cis or cis → trans conversion on Cu(111) can be induced in an unidirectional fashion by injecting tunneling electrons from the STM tip or heating the surface, respectively. We find that the cis ↔ cis tautomerization on Cu(111) occurs spontaneously via tunneling, verified by the negligible temperature dependence of the tautomerization rate below ˜23 K. Van der Waals corrected DFT calculations are used to characterize the adsorption structures of porphycene and to map the potential energy surface of the tautomerization on Cu(111). The calculated barriers are too high to be thermally overcome at cryogenic temperatures used in the experiment and zero-point energy corrections do not change this picture, leaving tunneling as the most likely mechanism. On Ag(111), the reversible trans ↔ cis conversion occurs spontaneously at 5 K and the cis ↔ cis tautomerization rate is much higher than on Cu(111), indicating a significantly smaller tautomerization barrier on Ag(111) due to the weaker interaction between porphycene and the surface compared to Cu(111). Additionally, the STM experiments and DFT calculations reveal that tautomerization on Cu(111) and Ag(111) occurs with migration of porphycene along the surface; thus, the translational motion couples with the tautomerization coordinate. On the other hand, the trans and cis configurations are not discernible in the STM image and no tautomerization is observed for porphycene on Au(111). The weak interaction of porphycene with Au(111) is closest to the gas-phase limit and therefore the absence

Oxygen-induced restructuring with release of gold atoms from Au(111)

International Nuclear Information System (INIS)

Min, B.K.; Deng, X.; Schalek, R.; Pinnaduwage, D.; Friend, C.M.

2005-01-01

Adsorption of oxygen atoms, achieved via electron-induced dissociation of nitrogen dioxide, induces restructuring of the 'herringbone' to a striped, soliton-wall structure accompanied by release of gold from the 'elbows' in the herringbone structure. The number density of 'elbows' (dislocations corresponding to a change in direction of the reconstruction) decreases as a function of increasing atomic oxygen coverage while the long range order observed in low energy electron diffraction (LEED) changes from (√(3)x22)-rec. to (1x22) in the limit of saturation coverage. Small islands and serrated step edges were formed due to the release of gold atoms from elbow sites of Au(111). The overall structural change of the Au(111) surface may result from the reduction of anisotropy related to the tensile stress relief of the Au(111) surface by oxygen atoms

Well-ordered structure of methylene blue monolayers on Au(111) surface: electrochemical scanning tunneling microscopy studies.

Science.gov (United States)

Song, Yonghai; Wang, Li

2009-02-01

Well-ordered structure of methylene blue (MB) monolayers on Au(111) surface has been successfully obtained by controlling the substrate potential. Electrochemical scanning tunneling microscopy (ECSTM) examined the monolayers of MB on Au(111) in 0.1 M HClO(4) and showed long-range ordered, interweaved arrays of MB with quadratic symmetry on the substrate in the potential range of double-layer charging. High-resolution ECSTM image further revealed the details of the MB monolayers structure of c(5 x 5 radical 3)rect and the flat-lying orientation of ad-molecules. The dependence of molecular organization on the substrate potential and the formation mechanism of well-ordered structure on Au(111) surface were investigated in detail. The obtained well-ordered structure at the interface between a metal and an aqueous electrolyte might possibly be used as high-density device for signal memory and templates for the advanced nanopatterning of surfaces. (c) 2008 Wiley-Liss, Inc.

Diffusion of 1,4-butanedithiol radicals on Au(111) and Au(100): A DFT-based comparison

Energy Technology Data Exchange (ETDEWEB)

Franke, Andreas; Pehlke, Eckhard [Institut fuer Theoretische Physik und Astrophysik, Universitaet Kiel, 24098 Kiel (Germany)

2010-07-01

Organic molecules chemisorbed on surfaces hold the perspective of surface functionalization. The 1,4-butanedithiol radical chemisorbed at the Au(111) or Au(100) surface serves as a model system for the S-Au molecule-substrate bond. Density functional total-energy calculations have been carried out for the chemisorption of the radical on the unreconstructed Au surfaces, which are both known to be stabilized under electrochemical conditions. Local minima with close-by energies indicate multi-valley potential-energy surfaces, which originate from the interplay between the two S-Au adsorbate-substrate bonds and the internal degrees of freedom of the butanedithiol radical. Diffusion paths of the radical on both Au surfaces have been calculated within DFT using VASP. The diffusion barriers for translation and rotation of the radical differ. They can be fine-tuned by varying the applied potential in the electrochemical cell. This is considered theoretically by inspecting the variation of the dipole moment along the reaction paths. Consequences for the dynamics of succeeding diffusion hops are discussed.

Electrochemical studies of Pu on prussian blue (PB)-gold nanoparticles (AuNPs) functionalized glassy carbon (GC) electrode

International Nuclear Information System (INIS)

Sharma, Manoj K.; Ambolikar, Arvind S.; Aggarwal, Suresh K.

2011-01-01

In electrochemical processes, electron transfer across the solid-liquid interface is the elementary step and electron transfer kinetics is significantly influenced by the interfacial properties. Therefore, preparation of well-defined electrochemical interface with highly controllable properties - larger effective surface area, increased mass transport, and better electronic interaction between the analyte and electrode - is significant for both fundamental and applied studies in electrochemistry. In the present work electrochemistry of Pu(IV)/Pu(III) is studied on multilayered AuNPs-PB-AuNPs functionalized electrode

Vanadium and molybdenum oxide thin films on Au(111). Growth and surface characterization

Energy Technology Data Exchange (ETDEWEB)

Guimond, Sebastien

2009-06-04

The growth and the surface structure of well-ordered V{sub 2}O{sub 3}, V{sub 2}O{sub 5} and MoO{sub 3} thin films have been investigated in this work. These films are seen as model systems for the study of elementary reaction steps occurring on vanadia and molybdena-based selective oxidation catalysts. It is shown that well-ordered V{sub 2}O{sub 3}(0001) thin films can be prepared on Au(111). The films are terminated by vanadyl groups which are not part of the V{sub 2}O{sub 3} bulk structure. Electron irradiation specifically removes the oxygen atoms of the vanadyl groups, resulting in a V-terminated surface. The fraction of removed vanadyl groups is controlled by the electron dose. Such surfaces constitute interesting models to probe the relative role of both the vanadyl groups and the undercoordinated V ions at the surface of vanadia catalysts. The growth of well-ordered V{sub 2}O{sub 5}(001) and MoO{sub 3}(010) thin films containing few point defects is reported here for the first time. These films were grown on Au(111) by oxidation under 50 mbar O{sub 2} in a dedicated high pressure cell. Contrary to some of the results found in the literature, the films are not easily reduced by annealing in UHV. This evidences the contribution of radiation and surface contamination in some of the reported thermal reduction experiments. The growth of ultrathin V{sub 2}O{sub 5} and MoO{sub 3} layers on Au(111) results in formation of interface-specific monolayer structures. These layers are coincidence lattices and they do not correspond to any known oxide bulk structure. They are assumed to be stabilized by electronic interaction with Au(111). Their formation illustrates the polymorphic character and the ease of coordination units rearrangement which are characteristic of both oxides. The formation of a second layer apparently precedes the growth of bulk-like crystallites for both oxides. This observation is at odds with a common assumption that crystals nucleate as soon as a

Vanadium and molybdenum oxide thin films on Au(111). Growth and surface characterization

International Nuclear Information System (INIS)

Guimond, Sebastien

2009-01-01

The growth and the surface structure of well-ordered V 2 O 3 , V 2 O 5 and MoO 3 thin films have been investigated in this work. These films are seen as model systems for the study of elementary reaction steps occurring on vanadia and molybdena-based selective oxidation catalysts. It is shown that well-ordered V 2 O 3 (0001) thin films can be prepared on Au(111). The films are terminated by vanadyl groups which are not part of the V 2 O 3 bulk structure. Electron irradiation specifically removes the oxygen atoms of the vanadyl groups, resulting in a V-terminated surface. The fraction of removed vanadyl groups is controlled by the electron dose. Such surfaces constitute interesting models to probe the relative role of both the vanadyl groups and the undercoordinated V ions at the surface of vanadia catalysts. The growth of well-ordered V 2 O 5 (001) and MoO 3 (010) thin films containing few point defects is reported here for the first time. These films were grown on Au(111) by oxidation under 50 mbar O 2 in a dedicated high pressure cell. Contrary to some of the results found in the literature, the films are not easily reduced by annealing in UHV. This evidences the contribution of radiation and surface contamination in some of the reported thermal reduction experiments. The growth of ultrathin V 2 O 5 and MoO 3 layers on Au(111) results in formation of interface-specific monolayer structures. These layers are coincidence lattices and they do not correspond to any known oxide bulk structure. They are assumed to be stabilized by electronic interaction with Au(111). Their formation illustrates the polymorphic character and the ease of coordination units rearrangement which are characteristic of both oxides. The formation of a second layer apparently precedes the growth of bulk-like crystallites for both oxides. This observation is at odds with a common assumption that crystals nucleate as soon as a monolayer is formed dur-ing the preparation of supported vanadia

Mesoscopic self-organization of a self-assembled supramolecular rectangle on highly oriented pyrolytic graphite and Au(111) surfaces.

Science.gov (United States)

Gong, Jian-Ru; Wan, Li-Jun; Yuan, Qun-Hui; Bai, Chun-Li; Jude, Hershel; Stang, Peter J

2005-01-25

A self-assembled supramolecular metallacyclic rectangle was investigated with scanning tunneling microscopy on highly oriented pyrolytic graphite and Au(111) surfaces. The rectangles spontaneously adsorb on both surfaces and self-organize into well ordered adlayers. On highly oriented pyrolytic graphite, the long edge of the rectangle stands on the surface, forming a 2D molecular network. In contrast, the face of the rectangle lays flat on the Au(111) surface, forming linear chains. The structures and intramolecular features obtained through high-resolution scanning tunneling microscopy imaging are discussed.

Bis(triisopropylsilylethynyl)pentacene/Au(111) interface: Coupling, molecular orientation, and thermal stability

KAUST Repository

Gnoli, Andrea; Ü stü nel, Hande; Toffoli, Daniele; Yu, Liyang; Catone, D.; Turchini, Stefano; Lizzit, Silvano; Stingelin, Natalie; Larciprê te, Rosanna

2014-01-01

The assembly and the orientation of functionalized pentacene at the interface with inorganics strongly influence both the electric contact and the charge transport in organic electronic devices. In this study electronic spectroscopies and theoretical modeling are combined to investigate the properties of the bis(triisopropylsilylethynyl)pentacene (TIPS-Pc)/Au(111) interface as a function of the molecular coverage to compare the molecular state in the gas phase and in the adsorbed phase and to determine the thermal stability of TIPS-Pc in contact with gold. Our results show that in the free molecule only the acene atoms directly bonded to the ligands are affected by the functionalization. Adsorption on Au(111) leads to a weak coupling which causes only modest binding energy shifts in the TIPS-Pc and substrate core level spectra. In the first monolayer the acene plane form an angle of 33 ± 2° with the Au(111) surface at variance with the vertical geometry reported for thicker solution-processed or evaporated films, whereas the presence of configurational disorder was observed in the multilayer. The thermal annealing of the TIPS-Pc/Au(111) interface reveals the ligand desorption at ∼470 K, which leaves the backbone of the decomposed molecule flat-lying on the metal surface as in the case of the unmodified pentacene. The weak interaction with the metal substrate causes the molecular dissociation to occur 60 K below the thermal decomposition taking place in thick drop-cast films.

Bis(triisopropylsilylethynyl)pentacene/Au(111) interface: Coupling, molecular orientation, and thermal stability

KAUST Repository

Gnoli, Andrea

2014-10-02

The assembly and the orientation of functionalized pentacene at the interface with inorganics strongly influence both the electric contact and the charge transport in organic electronic devices. In this study electronic spectroscopies and theoretical modeling are combined to investigate the properties of the bis(triisopropylsilylethynyl)pentacene (TIPS-Pc)/Au(111) interface as a function of the molecular coverage to compare the molecular state in the gas phase and in the adsorbed phase and to determine the thermal stability of TIPS-Pc in contact with gold. Our results show that in the free molecule only the acene atoms directly bonded to the ligands are affected by the functionalization. Adsorption on Au(111) leads to a weak coupling which causes only modest binding energy shifts in the TIPS-Pc and substrate core level spectra. In the first monolayer the acene plane form an angle of 33 ± 2° with the Au(111) surface at variance with the vertical geometry reported for thicker solution-processed or evaporated films, whereas the presence of configurational disorder was observed in the multilayer. The thermal annealing of the TIPS-Pc/Au(111) interface reveals the ligand desorption at ∼470 K, which leaves the backbone of the decomposed molecule flat-lying on the metal surface as in the case of the unmodified pentacene. The weak interaction with the metal substrate causes the molecular dissociation to occur 60 K below the thermal decomposition taking place in thick drop-cast films.

Evolution of magnetism of Cr nanoclusters on a Au(111) surface

Science.gov (United States)

Gotsis, Harry; Kioussis, Nicholas; Papaconstantopoulos, Dimitri

2004-03-01

Advances in low-temperature scanning tunneling microscopy under ultrahigh vacuum have provided new opportunities for investigating the magnetic structures of nanoclusters adsorbed on surfaces. Recent STM studies of Cr trimers on the Au(111) surface suggest a switching between two distinct electronic states. We have carried out ab initio electronic structure calculations to investigate the structural, electronic and magnetic properties of isolated Cr atoms, Cr dimers and trimers in different geometry. We will present results for the evolution of magnetic behavior including noncollinear magnetism and provide insight in the connection between magnetism and geometry.

A periodic mixed gaussians-plane waves DFT study on simple thiols on Au(111): adsorbate species, surface reconstruction, and thiols functionalization.

Science.gov (United States)

Rajaraman, Gopalan; Caneschi, Andrea; Gatteschi, Dante; Totti, Federico

2011-03-07

Here we present DFT calculations based on a periodic mixed gaussians/plane waves approach to study the energetics, structure, bonding of SAMs of simple thiols on Au(111). Several open issues such as structure, bonding and the nature of adsorbate are taken into account. We started with methyl thiols (MeSH) on Au(111) to establish the nature of the adsorbate. We have considered several structural models embracing the reconstructed surface scenario along with the MeS˙-Au(ad)-MeS˙ type motif put forward in recent years. Our calculations suggest a clear preference for the homolytic cleavage of the S-H bond leading to a stable MeS˙ on a gold surface. In agreement with the recent literature studies, the reconstructed models of the MeS˙ species are found to be energetically preferred over unreconstructed models. Besides, our calculations reveal that the model with 1:2 Au(ad)/thiols ratio, i.e. MeS˙-Au(ad)-MeS˙, is energetically preferred compared to the clean and 1:1 ratio models, in agreement with the experimental and theoretical evidences. We have also performed Molecular Orbital/Natural Bond Orbital, MO/NBO, analysis to understand the electronic structure and bonding in different structural motifs and many useful insights have been gained. Finally, the studies have then been extended to alkyl thiols of the RSR' (R, R' = Me, Et and Ph) type and here our calculations again reveal a preference for the RS˙ type species adsorption for clean as well as for reconstructed 1:2 Au(ad)/thiols ratio models.

Interfacial Electrochemical Electron Transfer Processes in Bacterial Biofilm Environments on Au(111)

DEFF Research Database (Denmark)

Hu, Yifan; Zhang, Jingdong; Ulstrup, Jens

2010-01-01

We have studied Streptococcus mutans (S. mutans) biolilm growth and growth inhibition on Au(111)-surfaces using atomic force microscopy (AFM) and interfacial electrochemistry of a number of redox probe molecules. AFM of the biofilm growth and growth inhibition on both mica and Au(111)-surfaces wa...

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

International Nuclear Information System (INIS)

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

2010-01-01

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

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

Science.gov (United States)

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

2014-07-21

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

Electron induced conformational changes of an imine-based molecular switch on a Au(111) surface

Energy Technology Data Exchange (ETDEWEB)

Lotze, Christian; Henningsen, Nils; Franke, Katharina; Schulze, Gunnar; Pascual, Jose Ignacio [Inst. f. Experimentalphysik, Freie Universitaet Berlin (Germany); Luo, Ying; Haag, Rainer [Inst. f. Organische Chemie, Freie Universitaet Berlin (Germany)

2009-07-01

Azobenzene-based molecules exhibit a cis-trans configurational photoisomerisation in solution. Recently, the adsorption properties of azobenzene derivatives have been investigated on different metal surfaces in order to explore the possible changes in the film properties induced by external stimuli. In azobenzene, the diazo-bridge is a key group for the isomerization process. Its interaction with a metal surface is dominated through the N lone-pair electrons, which reduces the efficiency of the conformational change. In order to reduce the molecule-surface interaction, we explore an alternative molecular architecture by substituting the diazo-bridge (-N=N-) of azobenzene by an imine-group (-N=CH-). We have investigated the imine-based compound para-carboxyl-di-benzene-imine (PCI) adsorbed on a Au(111) surface. The carboxylic terminations mediates the formation of strongly bonded molecular dimers, which align in ordered rows preferentially following the fcc regions of the Au(111) herringbone reconstruction. Low temperature scanning tunneling microscopy was used to induce conformational changes between trans and cis state of individual molecules in a molecular monolayer.

Investigation of Streptococcus mutans biofilm growth on modified Au(111)-surfaces using AFM and electrochemistry

DEFF Research Database (Denmark)

Hu, Yifan; Zhang, Jingdong; Ulstrup, Jens

2011-01-01

Biofilms of the bacterium Streptococcus mutans constitute perhaps the most important direct cause of human dental caries formation. We have studied S. mutans biofilm formation and properties on Au(111)-surfaces modified by self-assembled molecular monolayers (SAMs) of different thiol-based molecu...

Atom distribution and interactions in Ag{sub x}Pt{sub 1-x} and Au{sub x}Pt{sub 1-x} surface alloys on Pt(111)

Energy Technology Data Exchange (ETDEWEB)

Roetter, Ralf T.; Bergbreiter, Andreas; Hoster, Harry E.; Behm, R. Juergen [Institute of Surface Chemistry and Catalysis, Ulm University, D-89069 Ulm (Germany)

2009-07-01

The atom distributions in Ag{sub x}Pt{sub 1-x}/Pt(111) and Au{sub x}Pt{sub 1-x}/Pt(111) surface alloys were studied by high resolution UHV-STM. These surfaces were prepared by submonolayer Ag (Au) metal deposition on Pt(111), followed by annealing at 900 K or 1000 K, respectively, which in both cases results in surface confined 2D alloys, with equilibrated distribution of the components. Both systems show a tendency towards two-dimensional clustering, which fits well to their known bulk immiscibility. Effective cluster interactions (ECIs) will be derived by a quantitative evaluation of the 2D atom distributions in the surface alloys. By comparing the ECIs for PtAg and PtAu on Pt(111), and considering that Ag and Au have almost similar lattice constants, the results allow conclusion on the physical origin of the tendency for clustering.

Coverage dependent molecular assembly of anthraquinone on Au(111)

Science.gov (United States)

DeLoach, Andrew S.; Conrad, Brad R.; Einstein, T. L.; Dougherty, Daniel B.

2017-11-01

A scanning tunneling microscopy study of anthraquinone (AQ) on the Au(111) surface shows that the molecules self-assemble into several structures depending on the local surface coverage. At high coverages, a close-packed saturated monolayer is observed, while at low coverages, mobile surface molecules coexist with stable chiral hexamer clusters. At intermediate coverages, a disordered 2D porous network interlinking close-packed islands is observed in contrast to the giant honeycomb networks observed for the same molecule on Cu(111). This difference verifies the predicted extreme sensitivity [J. Wyrick et al., Nano Lett. 11, 2944 (2011)] of the pore network to small changes in the surface electronic structure. Quantitative analysis of the 2D pore network reveals that the areas of the vacancy islands are distributed log-normally. Log-normal distributions are typically associated with the product of random variables (multiplicative noise), and we propose that the distribution of pore sizes for AQ on Au(111) originates from random linear rate constants for molecules to either desorb from the surface or detach from the region of a nucleated pore.

Voltammetry and In Situ Scanning Tunnelling Microscopy of De Novo Designed Heme Protein Monolayers on Au(111)-Electrode Surfaces

DEFF Research Database (Denmark)

Albrecht, Tim; Li, Wu; Haehnel, Wolfgang

2006-01-01

to the tunnelling current, apparently due to slow electron transfer kinetics. As a consequence, STM images of heme-containing and heme-free MOP-C did not reveal any notable differences in apparent height or physical extension. The apparent height of heme-containing MOP-C did not show any dependence on the substrate...... potential being varied around the redox potential of the protein. The mere presence of an accessible molecular energy level is not sufficient to result in detectable tunnelling current modulation. (c) 2006 Elsevier B.V. All rights reserved.......In the present work, we report the electrochemical characterization and in situ scanning tunnelling microscopy (STM) studies of monolayers of an artificial de novo designed heme protein MOP-C, covalently immobilized on modified Au(111) surfaces. The protein forms closely packed monolayers, which...

A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111)

DEFF Research Database (Denmark)

O'Boyle, N.M.; Albrecht, Tim; Murgida, D.H.

2007-01-01

We present a density functional theory (DFT) study of an osmium polypyridyl complex adsorbed on Au(111). The osmium polypyridyl complex [Os(bpy)(2)(P0P)Cl](n+) [bpy is 2,2'-bipyridine, P0P is 4,4'-bipyridine, n = 1 for osmium(II), and n = 2 for osmium(III)] is bound to the surface through the fre...

Surface chemistry of 2-butanol and furfural on Cu, Au and Cu/Au single crystals

OpenAIRE

Megginson, Rory

2016-01-01

In this study, the adsorption of 2-butanol and furfural was investigated on Au (111), Cu (111) and Cu/Au (111) surfaces. It was hoped that by studying how these species adsorbed on these surfaces , insight would be provided into the roles of Cu and Au in the “hydrogen free” hydrogenation of furfural to furfuryl alcohol. This is a valuable process as currently furfuryl alcohol is derived from crude oil but it is possible to derive furfural from corn husk making it a greener process...

Reusable urine glucose sensor based on functionalized graphene oxide conjugated Au electrode with protective layers

Directory of Open Access Journals (Sweden)

Hye Youn Kim

2014-09-01

Full Text Available An electrochemical based system with multiple layers coated on a functionalized graphene oxide Au electrode was developed to measure glucose concentration in urine in a more stable way. Two types of gold printed circuit boards were fabricated and graphene oxide was immobilized on their surface by chemical adsorption. Multiple layers, composed of a couple of polymers, were uniformly coated on the surface electrode. This device exhibited higher electrochemical responses against glucose, a greater resistivity in the presence of interferential substances in urine, and durable stabilities for longer periods of time than conventional units. The efficiency in current level according to the order and ratio of solution was evaluated during the immobilization of the layer. The fabricated electrodes were then also evaluated using hyperglycemic clinical samples and compared with the patterns of blood glucose measured with commercially available glucose meters. Our findings show that not only was their pattern similar but this similarity is well correlated.

Extraordinary epitaxial alignment of graphene islands on Au(111)

International Nuclear Information System (INIS)

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

2012-01-01

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

Potential dependent adhesion forces on bare and underpotential deposition modified electrode surfaces

Energy Technology Data Exchange (ETDEWEB)

Serafin, J.M.; Hsieh, S.J.; Monahan, J.; Gewirth, A.A. [Univ. of Illinois, Urbana, IL (United States)

1998-12-03

Adhesion force measurements are used to determine the potential dependence of the force of adhesion between a Si{sub 3}N{sub 4} cantilever and a Au(111) surface modified by the underpotential deposition (upd) of Bi or Cu in acid solution or by oxide formation. The measured work of adhesion is near zero for most of the potential region examined in Bi upd but rises after the formation of a full Bi monolayer. The work of adhesion is high at positive potentials for Cu upd but then decreases as the Cu partial and full monolayers are formed. The work of adhesion is low in the oxide region on Au(111) but rises following the sulfate disordering transition at 1.1 V vs NHE. These results are interpreted in terms of the degree of solvent order on the electrode surface.

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

Directory of Open Access Journals (Sweden)

Benedikt Uhl

2013-12-01

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

Manipulation and control of a single molecular rotor on Au (111) surface

International Nuclear Information System (INIS)

Hai-Gang, Zhang; Jin-Hai, Mao; Qi, Liu; Nan, Jiang; Hai-Tao, Zhou; Hai-Ming, Guo; Dong-Xia, Shi; Hong-Jun, Gao

2010-01-01

Three different methods are used to manipulate and control phthalocyanine based single molecular rotors on Au (111) surface: (1) changing the molecular structure to alter the rotation potential; (2) using the tunnelling current of the scanning tunnelling microscope (STM) to change the thermal equilibrium of the molecular rotor; (3) artificial manipulation of the molecular rotor to switch the rotation on or off by an STM tip. Furthermore, a molecular 'gear wheel' is successfully achieved with two neighbouring molecules. (cross-disciplinary physics and related areas of science and technology)

Surface Structures and Thermal Desorption Behaviors of Cyclopentanethiol Self-Assembled Monolayers on Au(111)

International Nuclear Information System (INIS)

Kang, Hun Gu; Kim, You Young; Park, Tae Sun; Noh, Jae Geun; Park, Joon B.; Ito, Eisuke; Hara, Masahiko

2011-01-01

The surface structures, adsorption conditions, and thermal desorption behaviors of cyclopentanethiol (CPT) self-assembled monolayers (SAMs) on Au(111) were investigated by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and thermal desorption spectroscopy (TDS). STM imaging revealed that although the adsorption of CPT on Au(111) at room temperature generates disordered SAMs, CPT molecules at 50 .deg. C formed well-ordered SAMs with a (2√3 x √5)R41".deg. packing structure. XPS measurements showed that CPT SAMs at room temperature were formed via chemical reactions between the sulfur atoms and gold surfaces. TDS measurements showed two dominant TD peaks for the decomposed fragments (C_5H_9 "+, m/e = 69) generated via C-S bond cleavage and the parent molecular species (C_5H_9SH"+, m/e = 102) derived from a recombination of the chemisorbed thiolates and hydrogen atoms near 440 K. Interestingly, dimerization of sulfur atoms in n-alkanethiol SAMs usually occurs during thermal desorption and the same reaction did not happen for CPT SAMs, which may be due to the steric hindrance of cyclic rings of the CPT molecules. In this study, we demonstrated that the alicyclic ring of organic thiols strongly affected the surface structure and thermal desorption behavior of SAMs, thus providing a good method for controlling chemical and physical properties of organic thiol SAMs

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

International Nuclear Information System (INIS)

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 (1x1) bulk termination and a (23x√ 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

Modification of Au and Si(111):H surfaces towards biological sensing

Energy Technology Data Exchange (ETDEWEB)

Zhang, Xin; Rappich, Joerg [Helmholtz-Zentrum Berlin fuer Materialien und Energie GmbH, Institut fuer Si Photovoltaik, Berlin (Germany); Sun, Guoguang; Hinrichs, Karsten; Rosu, Dana; Esser, Norbert [ISAS-Institute for Analytical Sciences, Department Berlin (Germany); Hovestaedt, Marc; Ay, Bernhard; Volkmer, Rudolf [Institut fuer Medizinische Immunologie, Charite Berlin, Berlin (Germany); Janietz, Silvia [Fraunhofer-Institut fuer Angewandte Polymerforschung, Golm (Germany)

2010-07-01

Within the topics to grow functional organic surfaces for biosensors we grafted carboxylbenzene, aminobenzene and maleimidobenzene onto Au and H-terminated Si surfaces by electrochemical deposition from 4-carboxylbenzene-diazonium tetrafluoroborate (4-CBDT), 4-aminobenzene-diazonium tetrafluoroborate (4-ABDT) and 4-maleimidobenzene-diazonium tetrafluoroborate (4-MBDT).The electron injection to the diazonium compound in solution (cathodic current) leads to the formation of intermediate radicals, which further react with the surface (Au or Si:H) and the respective molecule is grafted onto the surface.The aim was to functionalise these surfaces for further reaction with corresponding amines, acids or cysteine-modified peptides. Ex-situ infrared spectroscopic ellipsometry (IRSE) was applied to inspect the surface species before and after the functionalisation.

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

KAUST Repository

Wu, Kunlin

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. © 2014 AIP Publishing LLC.

Surface Structures and Thermal Desorption Behaviors of Cyclopentanethiol Self-Assembled Monolayers on Au(111)

Energy Technology Data Exchange (ETDEWEB)

Kang, Hun Gu; Kim, You Young; Park, Tae Sun; Noh, Jae Geun [Hanyang University, Seoul (Korea, Republic of); Park, Joon B. [Chonbuk National University, Jeonju (Korea, Republic of); Ito, Eisuke; Hara, Masahiko [RIKEN-HYU Collaboration Center, Saitama (Japan)

2011-04-15

The surface structures, adsorption conditions, and thermal desorption behaviors of cyclopentanethiol (CPT) self-assembled monolayers (SAMs) on Au(111) were investigated by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and thermal desorption spectroscopy (TDS). STM imaging revealed that although the adsorption of CPT on Au(111) at room temperature generates disordered SAMs, CPT molecules at 50 .deg. C formed well-ordered SAMs with a (2√3 x √5)R41{sup .}deg. packing structure. XPS measurements showed that CPT SAMs at room temperature were formed via chemical reactions between the sulfur atoms and gold surfaces. TDS measurements showed two dominant TD peaks for the decomposed fragments (C{sub 5}H{sub 9} {sup +}, m/e = 69) generated via C-S bond cleavage and the parent molecular species (C{sub 5}H{sub 9}SH{sup +}, m/e = 102) derived from a recombination of the chemisorbed thiolates and hydrogen atoms near 440 K. Interestingly, dimerization of sulfur atoms in n-alkanethiol SAMs usually occurs during thermal desorption and the same reaction did not happen for CPT SAMs, which may be due to the steric hindrance of cyclic rings of the CPT molecules. In this study, we demonstrated that the alicyclic ring of organic thiols strongly affected the surface structure and thermal desorption behavior of SAMs, thus providing a good method for controlling chemical and physical properties of organic thiol SAMs.

Substrate induced ordering of molecular adsorbates on Au(111)

International Nuclear Information System (INIS)

Schott, J.H.; White, H.S.; Arana, C.R.

1992-01-01

Using scanning tunneling microscopy in dimethylformate, [Ru(bpy) 2 (bpy-(CH 2 ) x -bpy) 2+ ] (x = 4 and 5) monolayers adsorbed on the unreconstructed and √3 x 22 reconstructed surfaces of Au(111) were imaged in this paper. The substrate had a highly ordered pattern on the reconstructed surface, but random spatial distribution on the unreconstructed surface. 17 refs., 3 figs

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

Energy Technology Data Exchange (ETDEWEB)

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.

Controlling the stereochemistry and regularity of butanethiol self-assembled monolayers on Au(111)

DEFF Research Database (Denmark)

Yan, Jiawei; Ouyang, Runhai; Jensen, Palle Skovhus

2014-01-01

The rich stereochemistry of the self-assembled monolayers (SAMs) of four butanethiols on Au(111) is described, the SAMs containing up to 12 individual C, S, or Au chiral centers per surface unit cell. This is facilitated by synthesis of enantiomerically pure 2-butanethiol (the smallest unsubstitu......The rich stereochemistry of the self-assembled monolayers (SAMs) of four butanethiols on Au(111) is described, the SAMs containing up to 12 individual C, S, or Au chiral centers per surface unit cell. This is facilitated by synthesis of enantiomerically pure 2-butanethiol (the smallest...... when R is achiral, while adatom binding leads to rectangular plane groups that suppress long-range expression of chirality. Binding as RS• also inhibits the pitting intrinsically associated with adatom binding, desirably producing more regularly structured SAMs....

Molecular monolayers and interfacial electron transfer of pseudomonas aeruginosa azurin on Au(111)

DEFF Research Database (Denmark)

Chi, Qijin; Zhang, Jingdong; Nielsen, Jens Ulrik

2000-01-01

disulfide group to form a monolayer. The adsorption of this protein on Au(111) via a gold-sulfur binding mode is further supported by XPS measurements. In situ STM images with molecular resolution have been recorded and show a dense monolayer organization of adsorbed azurin molecules. Direct electron......We provide a comprehensive approach to the formation and characterization of molecular monolayers of the blue copper protein Pseudomonas aeruginosa azurin on Au(111) in aqueous ammonium acetate solution. Main issues are adsorption patterns, reductive desorption, properties of the double layer......, and long-range electrochemical electron transfer between the electrode and the copper center. Voltammetry, electrochemical impedance spectroscopy (EIS), in situ scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS) have been employed to disclose features of these issues. Zn...

Annealing temperature effect on self-assembled Au droplets on Si (111).

Science.gov (United States)

Sui, Mao; Li, Ming-Yu; Kim, Eun-Soo; Lee, Jihoon

2013-12-13

We investigate the effect of annealing temperature on self-assembled Au droplets on Si (111). The annealing temperature is systematically varied while fixing other growth parameters such as deposition amount and annealing duration clearly to observe the annealing temperature effect. Self-assembled Au droplets are fabricated by annealing from 50°C to 850°C with 2-nm Au deposition for 30 s. With increased annealing temperatures, Au droplets show gradually increased height and diameter while the density of droplets progressively decreases. Self-assembled Au droplets with fine uniformity can be fabricated between 550°C and 800°C. While Au droplets become much larger with increased deposition amount, the extended annealing duration only mildly affects droplet size and density. The results are systematically analyzed with cross-sectional line profiles, Fourier filter transform power spectra, height histogram, surface area ratio, and size and density plots. This study can provide an aid point for the fabrication of nanowires on Si (111).

Molecular dynamics and energy landscape of decanethiolates in self-assembled monolayers on Au(111) by STM

NARCIS (Netherlands)

Sotthewes, Kai; Wu, Hairong; Kumar, Avijit; Vancso, Gyula J.; Schön, Peter Manfred; Zandvliet, Henricus J.W.

2013-01-01

The energetics and dynamics of the various phases of decanethiolate self-assembled monolayers on Au(111) surfaces were studied with scanning tunneling microscopy. We have observed five different phases of the decanethiolate monolayer on Au(111): four ordered phases (β, δ, χ*, and ) and one

An SFG and DFG investigation of polycrystalline Au, Au-Cu and Au-Ag-Cu electrodes in contact with aqueous solutions containing KCN

International Nuclear Information System (INIS)

Bozzini, Benedetto; Busson, Bertrand; De Gaudenzi, Gian Pietro; Mele, Claudio; Tadjeddine, Abderrahmane

2007-01-01

In this paper, the behaviour of polycrystalline Au, Au-Cu (Cu 25%) and Au-Ag-Cu (Ag 10%, Cu 15%) electrodes in contact with neutral aqueous solutions of KCN has been studied as a function of potential by means of in situ sum frequency generation (SFG) and difference frequency generation (DFG) spectroscopies. The potential-dependent spectra have been analysed quantitatively with a model for the second-order non-linear susceptibility accounting for vibrational and electronic effects. The potential-dependence of the CN - stretching band position and of the free-electron contribution to the real part of the non-resonant component of the second-order susceptibility have been accounted for. Spectroelectrochemical results were complemented by cyclic voltammetric measurements. The chief stress in this work has been placed on systematising and quantifying the interaction between the vibrational and electronic structures of the electrodic interfaces studied. The effects of adsorbates on the electronic structure of the adsorbing electrode, as a function of electrode alloy composition and applied potential are particularly critical for the understanding of Au-alloy electrochemistry in the presence of cyanide and cyanocomplexes. The systematic comparison of SFG and DFG spectra measured under the same electrochemical conditions for Au, Au-Cu and Au-Ag-Cu electrodes discloses a rich phenomenology related to the electronic structure of the interface

An SFG and DFG investigation of polycrystalline Au, Au-Cu and Au-Ag-Cu electrodes in contact with aqueous solutions containing KCN

Energy Technology Data Exchange (ETDEWEB)

Bozzini, Benedetto [Dipartimento di Ingegneria dell' Innovazione, Universita di Lecce, v. Monteroni, I-73100 Lecce (Italy)]. E-mail: benedetto.bozzini@unile.it; Busson, Bertrand [CLIO-LCP, Universite Paris-Sud, 91405 Orsay Cedex (France); De Gaudenzi, Gian Pietro [Dipartimento di Ingegneria dell' Innovazione, Universita di Lecce, v. Monteroni, I-73100 Lecce (Italy); Mele, Claudio [Dipartimento di Ingegneria dell' Innovazione, Universita di Lecce, v. Monteroni, I-73100 Lecce (Italy); Tadjeddine, Abderrahmane [UDIL-CNRS, Bat. 201, Centre Universitaire Paris-Sud, BP 34, 91898 Orsay Cedex (France)

2007-01-16

In this paper, the behaviour of polycrystalline Au, Au-Cu (Cu 25%) and Au-Ag-Cu (Ag 10%, Cu 15%) electrodes in contact with neutral aqueous solutions of KCN has been studied as a function of potential by means of in situ sum frequency generation (SFG) and difference frequency generation (DFG) spectroscopies. The potential-dependent spectra have been analysed quantitatively with a model for the second-order non-linear susceptibility accounting for vibrational and electronic effects. The potential-dependence of the CN{sup -} stretching band position and of the free-electron contribution to the real part of the non-resonant component of the second-order susceptibility have been accounted for. Spectroelectrochemical results were complemented by cyclic voltammetric measurements. The chief stress in this work has been placed on systematising and quantifying the interaction between the vibrational and electronic structures of the electrodic interfaces studied. The effects of adsorbates on the electronic structure of the adsorbing electrode, as a function of electrode alloy composition and applied potential are particularly critical for the understanding of Au-alloy electrochemistry in the presence of cyanide and cyanocomplexes. The systematic comparison of SFG and DFG spectra measured under the same electrochemical conditions for Au, Au-Cu and Au-Ag-Cu electrodes discloses a rich phenomenology related to the electronic structure of the interface.

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

Energy Technology Data Exchange (ETDEWEB)

Llave, Ezequiel de la; Herrera, Santiago E.; Adam, Catherine; Méndez De Leo, Lucila P.; Calvo, Ernesto J.; Williams, Federico J., E-mail: fwilliams@qi.fcen.uba.ar [INQUIMAE-CONICET, Departamento de Química Inorgánica, Analítica y Química-Física, Facultad Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, Buenos Aires C1428EHA (Argentina)

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.

Ammonia synthesis on Au modified Fe(111) and Ag and Cu modified Fe(100) surfaces

DEFF Research Database (Denmark)

Lytken, Ole; Waltenburg, Hanne Neergaard; Chorkendorff, Ib

2003-01-01

In order to investigate any influence of steps and possible positive effects of making surface alloys the ammonia synthesis has been investigated over Au modified Fe(111) and Ag and Cu modified Fe(100) single crystals in the temperature range 603-773 K, using a system combining ultra-high vacuum...... and a high-pressure cell. Ammonia was synthesized from a stoichiometric (N-2:3H(2)) gas mixture at a pressure of 2 bar. By deposition of small amounts of An, the ammonia production activity of the Fe(1 1 1) surface can be enhanced. More important, for the gold modified surface, the reaction order in ammonia...

Monolayers of a De Novo Designed 4-Alpha-Helix Bundle Carboprotein and Partial Structures on Au(111)-Surfaces

DEFF Research Database (Denmark)

Brask, Jesper; Wackerbarth, Hainer; Jensen, Knud Jørgen

2002-01-01

on a galactopyranoside derivative with a thiol anchor aglycon suitable for surface immobilization on gold. The galactopyranoside with thiol anchor and the thiol anchor alone were prepared for comparison. Voltammetry of the three molecules on Au(111) showed reductive desorption peaks caused by monolayer adsorption via...... thiolate-Au bonding. In situ STM of the thiol anchor disclosed an ordered adlayer with clear domains and molecular features. This holds promise, broadly for single-molecule voltammetry and the SPM and scanning tunnelling microscopy (STM) of natural and synthetic proteins....

N-Heterocyclic carbenes on close-packed coinage metal surfaces: bis-carbene metal adatom bonding scheme of monolayer films on Au, Ag and Cu.

Science.gov (United States)

Jiang, Li; Zhang, Bodong; Médard, Guillaume; Seitsonen, Ari Paavo; Haag, Felix; Allegretti, Francesco; Reichert, Joachim; Kuster, Bernhard; Barth, Johannes V; Papageorgiou, Anthoula C

2017-12-01

By means of scanning tunnelling microscopy (STM), complementary density functional theory (DFT) and X-ray photoelectron spectroscopy (XPS) we investigate the binding and self-assembly of a saturated molecular layer of model N -heterocyclic carbene (NHC) on Cu(111), Ag(111) and Au(111) surfaces under ultra-high vacuum (UHV) conditions. XPS reveals that at room temperature, coverages up to a monolayer exist, with the molecules engaged in metal carbene bonds. On all three surfaces, we resolve similar arrangements, which can be interpreted only in terms of mononuclear M(NHC) 2 (M = Cu, Ag, Au) complexes, reminiscent of the paired bonding of thiols to surface gold adatoms. Theoretical investigations for the case of Au unravel the charge distribution of a Au(111) surface covered by Au(NHC) 2 and reveal that this is the energetically preferential adsorption configuration.

Physisorption of three amine terminated molecules (TMBDA, BDA, TFBDA) on the Au(111) Surface: The Role of van der Waals Interaction

Science.gov (United States)

Aminpour, Maral; Le, Duy; Rahman, Talat S.

2012-02-01

Recently, the electronic properties and alignment of tetramethyl-1,4-benzenediamine (TMBDA), 1,4-benzenediamine (BDA) and tetrafluro-1,4-benzenediamine (TFBDA) molecules were studied experimentally. Discrepancies were found for both the binding energy and the molecule tilt angle with respect to the surface, when results were compared with density functional theory calculations [1]. We have included the effect of vdW interactions both between the molecules and the Au(111) surface and find binding energies which are in very good agreement with experiments. We also find that at low coverages each of these molecules would adsorb almost parallel to the surface. N-Au bond lengths and charge redistribution on adsorption of the molecules are also analyzed. Our calculations are based on DFT using vdW-DF exchange correlation functionals. For BDA (since we are aware of experimental data), we show that for higher coverage, inclusion of intermolecular van der Waals interaction leads to tilting of the molecules with respect to the surface and formation of line structures. Our results demonstrate the central role played by intermolecular interaction in pattern formation on this surface.[4pt] [1] M. Dell'Angela et al, Nano Lett. 2010, 10, 2470; M. Kamenetska et al, J. Phys. Chem. C, 2011, 115, 12625

Surface characterization of sulfur and alkanethiol self-assembled monolayers on Au(111)

International Nuclear Information System (INIS)

Vericat, C; Vela, M E; Benitez, G A; Gago, J A Martin; Torrelles, X; Salvarezza, R C

2006-01-01

In the last two decades surface science techniques have decisively contributed to our present knowledge of alkanethiol self-assembled monolayers (SAMs) on solid surfaces. These organic layers have been a challenge for surface scientists, in particular because of the soft nature of the organic material (which can be easily damaged by irradiation), the large number of atoms present in the molecules, and the complex physical chemistry involved in the self-assembly process. This challenge has been motivated by the appealing technological applications of SAMs that cover many fields of the emerging area of nanotechnology. Sulfur (S) is closely related to alkanethiols and can be used to understand basic aspects of the surface structure of SAMs. In this review we focus on the atomic/molecular structures of S-containing SAMs on Au(111). Particular emphasis is given to the substrate, adsorption sites, chemical state of the S-metal bond and also to the experimental and theoretical tools used to study these structures at the atomic or molecular levels. (topical review)

Surface characterization of sulfur and alkanethiol self-assembled monolayers on Au(111)

Energy Technology Data Exchange (ETDEWEB)

Vericat, C [Instituto de Investigaciones FisicoquImicas Teoricas y Aplicadas (INIFTA), Universidad Nacional de La Plata-CONICET, Sucursal 4 Casilla de Correo 16 (1900) La Plata (Argentina); Vela, M E [Instituto de Investigaciones FisicoquImicas Teoricas y Aplicadas (INIFTA), Universidad Nacional de La Plata-CONICET, Sucursal 4 Casilla de Correo 16 (1900) La Plata (Argentina); Benitez, G A [Instituto de Investigaciones FisicoquImicas Teoricas y Aplicadas (INIFTA), Universidad Nacional de La Plata-CONICET, Sucursal 4 Casilla de Correo 16 (1900) La Plata (Argentina); Gago, J A Martin [Centro de AstrobiologIa (CSIC-INTA), 28850 Torrejon de Ardoz Madrid (Spain); Torrelles, X [Instituto de Ciencia de Materiales de Barcelona (ICMAB), Barcelona (Spain); Salvarezza, R C [Instituto de Investigaciones FisicoquImicas Teoricas y Aplicadas (INIFTA), Universidad Nacional de La Plata-CONICET, Sucursal 4 Casilla de Correo 16 (1900) La Plata (Argentina)

2006-12-06

In the last two decades surface science techniques have decisively contributed to our present knowledge of alkanethiol self-assembled monolayers (SAMs) on solid surfaces. These organic layers have been a challenge for surface scientists, in particular because of the soft nature of the organic material (which can be easily damaged by irradiation), the large number of atoms present in the molecules, and the complex physical chemistry involved in the self-assembly process. This challenge has been motivated by the appealing technological applications of SAMs that cover many fields of the emerging area of nanotechnology. Sulfur (S) is closely related to alkanethiols and can be used to understand basic aspects of the surface structure of SAMs. In this review we focus on the atomic/molecular structures of S-containing SAMs on Au(111). Particular emphasis is given to the substrate, adsorption sites, chemical state of the S-metal bond and also to the experimental and theoretical tools used to study these structures at the atomic or molecular levels. (topical review)

The electro-oxidation of the mixture of formaldehyde and 2-propanol on gold (100 and (111 single crystal planes in alkaline medium

Directory of Open Access Journals (Sweden)

BRANISLAV Z. NIKOLIC

2000-12-01

Full Text Available The effect of formaldehyde on the oxidation of 2-propanol and vice versa on gold single crystal planes (100 and 111 was studied. An activating effect in the reaction of the simultaneous oxidation of 2-propanol and formaldehyde was obtained on a gold (100 plane. In the case of a gold (111 electrode, the activation effect was not obtained. It was concluded that the adsorption of formaldehyde on the electrode surface prevents the adsorption of poisoning species formed during the electro-oxidation of 2-propanol on the Au(100 plane, while this is not the case on the Au(111 plane. The different behaviour is caused by the difference in the symmetry of the surface atoms of these two Au single-crystal planes.

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

Science.gov (United States)

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

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

Energy Technology Data Exchange (ETDEWEB)

Walen, Holly, E-mail: hwalen@iastate.edu [Department of Chemistry, Iowa State University, Ames, Iowa 50011 (United States); Liu, Da-Jiang [Ames Laboratory of the USDOE, Ames, Iowa 50011 (United States); Oh, Junepyo; Lim, Hyunseob; Kim, Yousoo [RIKEN Surface and Interface Science Laboratory, Wako, Saitama 351-0198 (Japan); Evans, J. W. [Ames Laboratory of the USDOE, Ames, Iowa 50011 (United States); Department of Physics and Astronomy, Iowa State University, Ames, Iowa 50011 (United States); Thiel, P. A. [Department of Chemistry, Iowa State University, Ames, Iowa 50011 (United States); Ames Laboratory of the USDOE, Ames, Iowa 50011 (United States); Department of Materials Science and Engineering, Iowa State University, Ames, Iowa 50011 (United States)

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.

Electrochemical Properties of Alkanethiol Monolayers Adsorbed on Nanoporous Au Surfaces

International Nuclear Information System (INIS)

Chu, Yeon Yi; Seo, Bora; Kim, Jong Won

2010-01-01

We investigated the electrochemical properties of alkanethiol monolayers adsorbed on NPG surfaces by cyclic voltammetry and electrochemical impedance spectroscopy, and the results are compared to those on flat Au surfaces. The reductive desorption of alkanethiols on NPG surfaces is observed in more negative potential regions than that on flat Au surfaces due the stronger S-Au interaction on NPG surfaces. While the electron transfer through alkanethiol monolayers on flat Au surfaces occurs via a tunneling process through the monolayer films, the redox species can permeate through the monolayers on NPG surfaces to transfer the electrons to the Au surfaces. The results presented here will help to elucidate the intrinsic electrochemical properties of alkanethiol monolayers adsorbed on curved Au surfaces, particularly on the surface of AuNPs. Self-assembled monolayers (SAMs) of thiolate molecules on Au surfaces have been the subject of intensive research for the last few decades due to their unique physical and chemical properties. The well-organized surface structures of thiolate SAMs with various end-group functionalities can be further utilized for many applications in biology and nanotechnology. In addition to the practical applications, SAMs of thiolate molecules on Au surfaces also provide unique opportunities to address fundamental issues in surface chemistry such as self-organized surface structures, electron transfer behaviors, and moleculesubstrate interactions. Although there have been numerous reports on the fundamental physical and chemical properties of thiolate SAMs on Au surfaces, most of them were investigated on flat Au surfaces, typically on well-defined Au(111) surfaces

Study of Alkylthiolate Self-assembled Monolayers on Au(111) Using a Semilocal meta-GGA Density Functional

DEFF Research Database (Denmark)

Ferrighi, Lara; Pan, Yun-xiang; Grönbeck, Henrik

2012-01-01

We present a density functional theory study of the structure and stability of self-assembled monolayers (SAMs) of alkylthiolate on Au(111) as a function of the alkyl chain length. The most favorable structure of the SAMs involves an RS–Au–SR complex (S being sulfur, R being an alkyl chain) forme....... In particular, the use of M06-L yields an increased stability of the SAMs with increasing alkyl chain length and an increased attractive interaction between RS–Au–SR complexes at shorter distances....... through sandwiching one Au adatom by two alkylthiolates (RSs). Comparing a generalized gradient (GGA-PBE) and a meta-GGA (MGGA-M06-L) exchange-correlation functional we find that only the meta-GGA functional predicts the experimentally observed attractive intermolecular interactions within the SAMs...

Vibrational properties of the Au-(√{3 }×√{3 } )/Si(111) surface reconstruction

Science.gov (United States)

Halbig, B.; Liebhaber, M.; Bass, U.; Geurts, J.; Speiser, E.; Räthel, J.; Chandola, S.; Esser, N.; Krenz, M.; Neufeld, S.; Schmidt, W. G.; Sanna, S.

2018-01-01

The vibrational properties of the Au-induced (√{3 }×√{3 })R 30∘ reconstruction of the Si(111) surface are investigated by polarized surface Raman spectroscopy and density-functional theory. The Raman measurements are performed in situ at room temperature as well as 20 K, and they reveal the presence of vibrational eigenmodes in the spectral range from 20 to 450 cm-1. In particular, two peaks of E symmetry at 75 and 183 cm-1 dominate the spectra. No substantial difference between room- and low-temperature spectra is observed, suggesting that the system does not undergo a phase transition down to 20 K. First-principles calculations are performed based on the structural models discussed in the literature. The thermodynamically stable conjugate honeycomb-chained-trimer model (CHCT) [Surf. Sci. 275, L691 (1992), 10.1016/0039-6028(92)90785-5] leads to phonon eigenvalues compatible with the experimental observations in the investigated spectral range. On the basis of the phonon eigenfrequencies, symmetries, and Raman intensities, we assign the measured spectral features to the calculated phonon modes. The good agreement between measured and calculated modes provides a strong argument in favor of the CHCT model.

Effects of Cu intercalation on the graphene/Ni(111) surface: density-functional calculations

International Nuclear Information System (INIS)

Kwon, Se Gab; Kang, Myung Ho

2012-01-01

The Cu-intercalated graphene/Ni(111) surface has been studied by using density-functional theory calculations. We find that (1) the intercalation-induced decoupling between graphene and the Ni(111) substrate begins sharply at a Cu coverage of about 0.75 ML, (2) at the optimal Cu coverage of 1 ML, graphene recovers an almost ideal Dirac-cone band structure with no band gap, and (3) the Dirac point is located at 0.17 eV below the Fermi level, indicating a small charge transfer from the substrate. Cu thus plays essentially the same role as Au in realizing quasi-free-standing graphene by intercalation. Our charge character analysis shows that the Dirac-cone bands near the Fermi level reveal a weakening of their π character when crossing the Ni d bands, suggesting that the resulting low Dirac-cone intensity could possibly be the origin of the recent photoemission report of a relatively large band gap of 0.18 eV.

Exotic high activity surface patterns in PtAu nanoclusters

KAUST Repository

Mokkath, Junais Habeeb

2013-05-09

The structure and chemical ordering of PtAu nanoclusters of 79, 135, and 201 atoms are studied via a combination of a basin hopping atom-exchange technique (to locate the lowest energy homotops at fixed composition), a symmetry orbit technique (to find the high symmetry isomers), and density functional theory local reoptimization (for determining the most stable homotop). The interatomic interactions between Pt and Au are derived from the empirical Gupta potential. The lowest energy structures show a marked tendency toward PtcoreAushell chemical ordering by enrichment of the more cohesive Pt in the core region and of Au in the shell region. We observe a preferential segregation of Pt atoms to (111) facets and Au atoms to (100) facets of the truncated octahedron cluster motif. Exotic surface patterns are obtained particularly for Pt-rich compositions, where Pt atoms are being surrounded by Au atoms. These surface arrangements boost the catalytic activity by creating a large number of active sites. © 2013 American Chemical Society.

Coexistence of multiple conformations in cysteamine monolayers on Au(111)

DEFF Research Database (Denmark)

Zhang, Jingdong; Bilic, A; Reimers, JR

2005-01-01

The structural organization, catalytic function, and electronic properties of cysteamine monolayers on Au(111) have been addressed comprehensively by voltammetry, in situ scanning tunneling microscopy (STM) in anaerobic environment, and a priori molecular dynamics (MD) simulation and STM image si...

Triptycene-terminated thiolate and selenolate monolayers on Au(111

Directory of Open Access Journals (Sweden)

Jinxuan Liu

2017-04-01

Full Text Available To study the implications of highly space-demanding organic moieties on the properties of self-assembled monolayers (SAMs, triptycyl thiolates and selenolates with and without methylene spacers on Au(111 surfaces were comprehensively studied using ultra-high vacuum infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy and thermal desorption spectroscopy. Due to packing effects, the molecules in all monolayers are substantially tilted. In the presence of a methylene spacer the tilt is slightly less pronounced. The selenolate monolayers exhibit smaller defect densities and therefore are more densely packed than their thiolate analogues. The Se–Au binding energy in the investigated SAMs was found to be higher than the S–Au binding energy.

Label-Free Electrochemical Detection of Vanillin through Low-Defect Graphene Electrodes Modified with Au Nanoparticles

Directory of Open Access Journals (Sweden)

Jingyao Gao

2018-03-01

Full Text Available Graphene is an excellent modifier for the surface modification of electrochemical electrodes due to its exceptional physical properties and, for the development of graphene-based chemical and biosensors, is usually coated on glassy carbon electrodes (GCEs via drop casting. However, the ease of aggregation and high defect content of reduced graphene oxides degrade the electrical properties. Here, we fabricated low-defect graphene electrodes by catalytically thermal treatment of HPHT diamond substrate, followed by the electrodeposition of Au nanoparticles (AuNPs with an average size of ≈60 nm on the electrode surface using cyclic voltammetry. The Au nanoparticle-decorated graphene electrodes show a wide linear response range to vanillin from 0.2 to 40 µM with a low limit of detection of 10 nM. This work demonstrates the potential applications of graphene-based hybrid electrodes for highly sensitive chemical detection.

Spin-polarized scanning tunneling spectroscopy of self-organized nanoscale Co islands on Au(111) surfaces.

Science.gov (United States)

Schouteden, K; Muzychenko, D A; Van Haesendonck, C

2008-07-01

Magnetic monolayer and bilayer Co islands of only a few nanometer in size were grown by atomic deposition on atomically flat Au(111) films. The islands were studied in situ by scanning tunneling microscopy (STM) and spectroscopy at low temperatures. Spin-resolved tunneling spectroscopy, using an STM tip with a magnetic coating, revealed that the Co islands exhibit a net magnetization perpendicular to the substrate surface due to the presence of spin-polarized d-states. A random distribution of islands with either upward or downward pointing magnetization was observed, without any specific correlation of magnetization orientation with island size or island height.

Dipole moments associated with edge atoms; a comparative study on stepped Pt, Au and W surfaces

International Nuclear Information System (INIS)

Besocke, K.; Krahl-Urban, B.; Wagner, H.

1977-01-01

Work function measurements have been performed on stepped Pt and Au surfaces with (111) terraces and on W surfaces with (110) terraces. In each case the work function decreases linearly with increasing step density and depends on the step orientation. The work function changes are attributed to dipole moments associated with the step edges. The dipole moments per unit step length are larger for open edge structures than for densely packed ones. The dipole moments for Pt are about twice as large as for Au and W. (Auth.)

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

Science.gov (United States)

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.

In-situ quartz crystal microgravimetric studies of molecular adsorbates containing thiol and hydroquinone moieties bound to Au(111) surfaces in aqueous electrolytes

Energy Technology Data Exchange (ETDEWEB)

Mo, Y.; Sukenik, C.; Sandifer, M. [Case Western Univ., Cleveland, OH (United States); Barriga, R.J.; Soriaga, M.P.; Scherson, D. [Texas A& M Univ., College Station, TX (United States)

1995-12-01

The microgravimetric properties of monolayers of 2, 5-dihydroxythiophenol, 2,5-dihydroxybenzyl mercaptan, and 2, 5-dihydroxy-4-methylbenzyl mercaptan adsorbed on Au(111) single crystal electrodes were examined by in situ quartz crystal microbalance techniques in aqueous perchloric acid electrolytes. The results obtained are consistent with the reversible loss of an average of about three waters per adsorbed molecule as the layers are oxidized and subsequently reduced. These observations provide evidence for discrete changes in the extent of bound water within the hydroquinone/quinone layer as the oxidation state of the monolayer is changed. 9 refs., 4 figs.

Surface Pourbaix diagrams and oxygen reduction activity of Pt, Ag and Ni(111) surfaces studied by DFT

DEFF Research Database (Denmark)

Hansen, Heine Anton; Rossmeisl, Jan; Nørskov, Jens Kehlet

2008-01-01

The electrochemical most stable surface structures is investigated as function of pH and potential for Pt, Ag and Ni based on DFT calculations and constructed surface Pourbaix diagrams. It is also explained why metals such as Ag and Ni may be used successfully in alkaline fuel cells but not in ac......The electrochemical most stable surface structures is investigated as function of pH and potential for Pt, Ag and Ni based on DFT calculations and constructed surface Pourbaix diagrams. It is also explained why metals such as Ag and Ni may be used successfully in alkaline fuel cells...... but not in acidic PEM fuel cells. Based on density functional theory calculations we investigate the electrochemically most stable surface structures as a function of pH and electrostatic potential for Pt(111), Ag(111) and Ni(111), and we construct surface Pourbaix diagrams. We study the oxygen reduction reaction......, on the other hand, is constant vs. the standard hydrogen electrode (SHE). For Ag, this means that where the potential for dissolution and ORR are about the same at pH = 0, Ag becomes more stable relative to RHE as pH is increased. Hence the pH dependent stability offers an explanation for the possible use...

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

International Nuclear Information System (INIS)

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

2014-01-01

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 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

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

Energy Technology Data Exchange (ETDEWEB)

Hernandez-Tamargo, Carlos E.; Montero-Alejo, Ana Lilian [Laboratory of Computational and Theoretical Chemistry (LQCT), Faculty of Chemistry, Havana University, Havana 10400 (Cuba); Pujals, Daniel Codorniu [Higher Institute of Technologies and Applied Sciences (InSTEC), Havana 10400 (Cuba); Mikosch, Hans [Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/E164-EC, 1060 Vienna (Austria); Hernández, Mayra P., E-mail: mayrap@imre.oc.uh.cu [Instituto de Ciencias y Tecnologías de Materiales (IMRE), Havana 10400 (Cuba)

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.

Solvent effects on the adsorption and self-organization of Mn12 on Au(111).

Science.gov (United States)

Pineider, Francesco; Mannini, Matteo; Sessoli, Roberta; Caneschi, Andrea; Barreca, Davide; Armelao, Lidia; Cornia, Andrea; Tondello, Eugenio; Gatteschi, Dante

2007-11-06

A sulfur-containing single molecule magnet, [Mn12O12(O2CC6H4SCH3)16(H2O)4], was assembled from solution on a Au(111) surface affording both submonolayer and monolayer coverages. The adsorbate morphology and the degree of coverage were inspected by scanning tunneling microscopy (STM), while X-ray photoelectron spectroscopy (XPS) allowed the determination of the chemical nature of the adsorbate on a qualitative and quantitative basis. The properties of the adsorbates were found to be strongly dependent on the solvent used to dissolve the magnetic complex. In particular, systems prepared from tetrahydrofuran solutions gave arrays of isolated and partially ordered clusters on the gold substrate, while samples prepared from dichloromethane exhibited a homogeneous monolayer coverage of the whole Au(111) surface. These findings are relevant to the optimization of magnetic addressing of single molecule magnets on surfaces.

Characterization of self-assembled electrodes based on Au-Pt nanoparticles for PEMFC application

Energy Technology Data Exchange (ETDEWEB)

Valenzuela, E. [Politecnica Univ. de Chiapas, Tuxtla Gutierrez, Chiapas (Mexico). Energia y Sustentabilidad; Sebastian, P.J. [Politecnica Univ. de Chiapas, Chiapas (Mexico). Energia y Sustentabilidad; Centro de Investigacion en Energia, UNAM, Morelos (Mexico); Gamboa, S.A. [Centro de Investigacion en Energia, UNAM, Morelos (Mexico); Pal, U. [Inst. de Fisica, Universidad Autonoma de Puebla Univ., Puebla (Mexico). Inst. de Fisica; Gonzalez, I. [Autonoma Metropolitana Univ. (Mexico). Dept. de Quimica

2008-07-01

This paper reported on a study in which membrane electrode assemblies (MEAs) were fabricated by depositing Au, Pt and AuPt nanoparticles on Nafion 115 membrane for use in a proton exchange membrane fuel cell (PEMFC). A Rotating Disc Electrode (RDE) was used to measure the nanoparticle catalyst activity. After deposition of the nanoparticles on the membrane, the surface was studied by Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). The membrane proton conduction process was studied by Electrochemical Impedance Spectroscopy (EIS) with the 4 probe technique. The MEAs fabricated with Nafion/Metal membranes were evaluated in a PEMFC under standard conditions. Colloidal solutions were used to prepare self-assembled electrodes with nanoparticles deposited on Nafion membrane. The particles deposited on Nafion showed good stability and had homogeneous distribution along the membrane surface. The impedance results revealed an increase in the membrane proton resistance of the self-assembled electrodes compared to unmodified Nafion. The Au-Pt nanoparticles were obtained by chemical reduction. The nanoparticle size in the three systems was about 2 nm. The self-assembled electrodes performed well in standard conditions. The optimum colloidal concentration and immersion time must be determined in order to obtain good catalytic activity and high membrane conductance. The self-assembled Nafion/AuPt had the best open circuit potential (887 mV). The Au and Pt self-assemblies showed a similar performance in terms of maximum power and maximum current density. The performance of the Nafion/Au self-assembly was influenced more by ohmic losses, particularly in the membrane. The maximum power generation was obtained at 0.35 V. The mass transport losses increased after this value, thereby affecting the efficiency of the PEMFC. 2 figs.

Simple and rapid mercury ion selective electrode based on 1-undecanethiol assembled Au substrate and its recognition mechanism

Energy Technology Data Exchange (ETDEWEB)

Li, Xian-Qing; Liang, Hai-Qing [Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, School of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410114 (China); Cao, Zhong, E-mail: zhongcao2004@163.com [Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, School of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410114 (China); Xiao, Qing [Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, School of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410114 (China); Xiao, Zhong-Liang, E-mail: xiaozhongliang@163.com [Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, School of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410114 (China); State Key Laboratory of High Performance Complex Manufacturing, School of Mechanical and Electrical Engineering, Central South University, Changsha 410083 (China); Song, Liu-Bin [Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, School of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410114 (China); Chen, Dan [Hunan Airbluer Environmental Protection Technology Co., Ltd., Changsha 410014 (China); Wang, Fu-Liang [State Key Laboratory of High Performance Complex Manufacturing, School of Mechanical and Electrical Engineering, Central South University, Changsha 410083 (China)

2017-03-01

A simple and rapid mercury ion selective electrode based on 1-undecanethiol (1-UDT) assembled Au substrate (Au/1-UDT) has been well constructed. 1-UDT was for the purpose of generating self-assembled monolayer on gold surface to recognize Hg{sup 2+} in aqueous solution, which had a working concentration range of 1.0 × 10{sup −} {sup 8}–1.0 × 10{sup −4} mol L{sup −1}, with a Nernst response slope of 28.83 ± 0.4 mV/-pC, a detection limit of 4.5 × 10{sup −9} mol L{sup −1}, and a good selectivity over the other tested cations. Also, the Au/1-UDT possessed good reproducibility, stability, and short response time. The recovery obtained for the determination of mercury ion in practical tremella samples was in the range of 99.8–103.4%. Combined electrochemical analysis and X-ray photoelectron spectroscopy (XPS) with quantum chemical computation, the probable recognition mechanism of the electrode for selective recognition of Hg{sup 2+} has been investigated. The covalent bond formed between mercury and sulfur is stronger than the one between gold and sulfur and thus prevents the adsorption of 1-UDT molecules on the gold surface. The quantum chemical computation with density functional theory further demonstrates that the strong interaction between the mercury atom and the sulfur atom on the gold surface leads to the gold sulfur bond ruptured and the gold mercury metallophilic interaction. - Highlights: • A simple and rapid mercury ion selective electrode has been well constructed. • The Au/1-UDT electrode for sensing Hg{sup 2+} has a sensitivity of 28.83 ± 0.4 mV/− pC. • The ISE method has a detection limit of Hg{sup 2+} down to 4.5 × 10{sup −9} mol L{sup −1}. • A mechanism with density functional theory for recognition of Hg{sup 2+} is developed. • The quantum chemical computation demonstrates Au-Hg metallophilic interaction.

Simultaneous determination of paracetamol and ascorbic acid using tetraoctylammonium bromide capped gold nanoparticles immobilized on 1,6-hexanedithiol modified Au electrode

International Nuclear Information System (INIS)

Nair, Santhosh S.; John, S. Abraham; Sagara, Takamasa

2009-01-01

Tetraoctylammonium bromide stabilized gold nanoparticles (TOAB-AuNPs) attached to 1,6-hexanedithiol (HDT) modified Au electrode was used for the simultaneous determination of paracetamol (PA) and ascorbic acid (AA) at physiological pH. The attachment of TOAB-AuNPs on HDT modified Au surface was confirmed by attenuated total reflectance (ATR)-FT-IR spectroscopy and atomic force microscope (AFM). The ATR-FT-IR spectrum of TOAB-AuNPs attached to the HDT monolayer showed a characteristic stretching modes corresponding to -CH 2 and -CH 3 of TOAB, confirming the immobilization of AuNPs with surface-protecting TOAB ions on the surface of the AuNPs after being attached to HDT modified Au electrode. AFM image showed that the immobilized AuNPs were spherical in shape and densely packed to a film of ca. 7 nm thickness. Interestingly, TOAB-AuNPs modified electrode shifted the oxidation potential of PA towards less positive potential by 70 mV and enhanced its oxidation current twice when compared to bare Au electrode. In addition, the AuNPs modified electrode separated the oxidation potentials of AA and PA by 210 mV, whereas bare Au electrode failed to resolve them. The amperometry current of PA was increased linearly from 1.50 x 10 -7 to 1.34 x 10 -5 M with a correlation coefficient of 0.9981 and the lowest detection limit was found to be 2.6 nM (S/N = 3). The present method was successfully used to determine the concentration of PA in human blood plasma and commercial drugs.

Simultaneous determination of paracetamol and ascorbic acid using tetraoctylammonium bromide capped gold nanoparticles immobilized on 1,6-hexanedithiol modified Au electrode

Energy Technology Data Exchange (ETDEWEB)

Nair, Santhosh S. [Department of Chemistry, Gandhigram Rural University, Gandhigram 624302, Dindigul (India); John, S. Abraham [Department of Chemistry, Gandhigram Rural University, Gandhigram 624302, Dindigul (India)], E-mail: abrajohn@yahoo.co.in; Sagara, Takamasa [Department of Chemistry, Gandhigram Rural University, Gandhigram 624302, Dindigul (India)], E-mail: sagara@nagasaki-u.ac.jp

2009-11-30

Tetraoctylammonium bromide stabilized gold nanoparticles (TOAB-AuNPs) attached to 1,6-hexanedithiol (HDT) modified Au electrode was used for the simultaneous determination of paracetamol (PA) and ascorbic acid (AA) at physiological pH. The attachment of TOAB-AuNPs on HDT modified Au surface was confirmed by attenuated total reflectance (ATR)-FT-IR spectroscopy and atomic force microscope (AFM). The ATR-FT-IR spectrum of TOAB-AuNPs attached to the HDT monolayer showed a characteristic stretching modes corresponding to -CH{sub 2} and -CH{sub 3} of TOAB, confirming the immobilization of AuNPs with surface-protecting TOAB ions on the surface of the AuNPs after being attached to HDT modified Au electrode. AFM image showed that the immobilized AuNPs were spherical in shape and densely packed to a film of ca. 7 nm thickness. Interestingly, TOAB-AuNPs modified electrode shifted the oxidation potential of PA towards less positive potential by 70 mV and enhanced its oxidation current twice when compared to bare Au electrode. In addition, the AuNPs modified electrode separated the oxidation potentials of AA and PA by 210 mV, whereas bare Au electrode failed to resolve them. The amperometry current of PA was increased linearly from 1.50 x 10{sup -7} to 1.34 x 10{sup -5} M with a correlation coefficient of 0.9981 and the lowest detection limit was found to be 2.6 nM (S/N = 3). The present method was successfully used to determine the concentration of PA in human blood plasma and commercial drugs.

Effects of pressure, temperature and atomic exchanges on phase separation dynamics in Au/Ni(111) surface alloy: Kinetic Monte Carlo study

Energy Technology Data Exchange (ETDEWEB)

Zvejnieks, G. [Institute for Solid State Physics, University of Latvia, Kengaraga 8, LV-1063 Riga (Latvia); Ibenskas, A., E-mail: ibenskas@pfi.lt [Center for Physical Sciences and Technology, Semiconductor Physics Institute, Gostauto 11, LT-01108 Vilnius (Lithuania); Tornau, E.E. [Center for Physical Sciences and Technology, Semiconductor Physics Institute, Gostauto 11, LT-01108 Vilnius (Lithuania)

2015-11-15

Instability of the Au/Ni(111) surface alloy is studied in different CO gas pressure, p, and temperature limits using kinetic Monte Carlo simulations. We analyze the reaction front dynamics and formation of Au clusters using the model which takes into account surface adatom pair and three-body interactions, CO adsorption and desorption, catalytic carbonyl formation reaction, Au and Ni adatom diffusion and their concerted exchange. Variation of interaction parameters allows us to identify three possible reaction front propagation limits with different pressure dependencies: (i) slow channel-like flow in agreement with experimental data [1] (step flow rate, R, increases with p), (ii) intermediate regime (weak p–dependence), and (iii) fast homogeneous flow (R decreases with p). We find that only Au–Ni exchange, contrary to both Ni–CO and Au–CO exchanges, significantly reduces the number of screened Ni atoms inside the Au clusters and stimulates the occurrence of Ni-free Au clusters. The size of Au islands depends on both pressure and temperature. At a fixed temperature it decreases with pressure due to an increased step flow rate. In the high temperature limit, despite the step flow rate exponential increase with temperature, the cluster size increases due to an enhanced Au mobility. - Highlights: • Kinetic Monte Carlo study of Au–Ni surface alloy instability to CO pressure and temperature. • Three reaction front propagation regimes. • In channel-like regime, the step flow rate increases with CO pressure as in experiment. • Ni-free Au islands are obtained when Au-Ni adatom exchange mechanism is considered. • The size of Au islands decreases with pressure and increases with temperature.

Effects of pressure, temperature and atomic exchanges on phase separation dynamics in Au/Ni(111) surface alloy: Kinetic Monte Carlo study

International Nuclear Information System (INIS)

Zvejnieks, G.; Ibenskas, A.; Tornau, E.E.

2015-01-01

Instability of the Au/Ni(111) surface alloy is studied in different CO gas pressure, p, and temperature limits using kinetic Monte Carlo simulations. We analyze the reaction front dynamics and formation of Au clusters using the model which takes into account surface adatom pair and three-body interactions, CO adsorption and desorption, catalytic carbonyl formation reaction, Au and Ni adatom diffusion and their concerted exchange. Variation of interaction parameters allows us to identify three possible reaction front propagation limits with different pressure dependencies: (i) slow channel-like flow in agreement with experimental data [1] (step flow rate, R, increases with p), (ii) intermediate regime (weak p–dependence), and (iii) fast homogeneous flow (R decreases with p). We find that only Au–Ni exchange, contrary to both Ni–CO and Au–CO exchanges, significantly reduces the number of screened Ni atoms inside the Au clusters and stimulates the occurrence of Ni-free Au clusters. The size of Au islands depends on both pressure and temperature. At a fixed temperature it decreases with pressure due to an increased step flow rate. In the high temperature limit, despite the step flow rate exponential increase with temperature, the cluster size increases due to an enhanced Au mobility. - Highlights: • Kinetic Monte Carlo study of Au–Ni surface alloy instability to CO pressure and temperature. • Three reaction front propagation regimes. • In channel-like regime, the step flow rate increases with CO pressure as in experiment. • Ni-free Au islands are obtained when Au-Ni adatom exchange mechanism is considered. • The size of Au islands decreases with pressure and increases with temperature

Azobenzene versus 3,3',5,5'-tetra-tert-butyl-azobenzene (TBA) at Au(111): characterizing the role of spacer groups.

Science.gov (United States)

McNellis, Erik R; Bronner, Christopher; Meyer, Jörg; Weinelt, Martin; Tegeder, Petra; Reuter, Karsten

2010-06-28

We present large-scale density-functional theory (DFT) calculations and temperature programmed desorption measurements to characterize the structural, energetic and vibrational properties of the functionalized molecular switch 3,3',5,5'-tetra-tert-butyl-azobenzene (TBA) adsorbed at Au(111). Particular emphasis is placed on exploring the accuracy of the semi-empirical dispersion correction approach to semi-local DFT (DFT-D) in accounting for the substantial van der Waals component in the surface bonding. In line with previous findings for benzene and pure azobenzene at coinage metal surfaces, DFT-D significantly overbinds the molecule, but seems to yield an accurate adsorption geometry as far as can be judged from the experimental data. Comparing the trans adsorption geometry of TBA and azobenzene at Au(111) reveals a remarkable insensitivity of the structural and vibrational properties of the -N[double bond, length as m-dash]N- moiety. This questions the established view of the role of the bulky tert-butyl-spacer groups for the switching of TBA in terms of a mere geometric decoupling of the photochemically active diazo-bridge from the gold substrate.

Laterally enhanced growth of electrodeposited Au to form ultrathin films on nonconductive surfaces

International Nuclear Information System (INIS)

Kobayashi, Chiaki; Saito, Mikiko; Homma, Takayuki

2012-01-01

We investigated the laterally enhanced growth of electrodeposited Au for fabricating nanogap electrodes. To enhance the lateral growth, we carried out electrodeposition over patterned electrodes onto a SiO 2 surface modified with self-assembled monolayers (SAMs) or dendrimers with amine groups. The morphology and thickness of the Au films were controlled by adjusting deposition conditions such as duration, applied potential, and Au ion concentration in the bath. To investigate the mechanism of the laterally enhanced growth, the surface states of SAM- or dendrimer-modified SiO 2 were analyzed by X-ray photoelectron spectroscopy (XPS). The XPS results indicate the existence of organic molecules and Au ions on the SiO 2 surface, which suggests that laterally enhanced growth is induced by the Au ions coordinated on the amine groups of the organic molecules. To further analyze the mechanism of the laterally enhanced growth, we investigated the relationship between the morphology of the laterally enhanced growth of Au and the amount of Au ions on organic molecules. The laterally enhanced growth of Au is expected to be useful for fabricating thin film nanogap electrodes.

Structure formation and surface chemistry of ionic liquids on model electrode surfaces—Model studies for the electrode | electrolyte interface in Li-ion batteries

Science.gov (United States)

Buchner, Florian; Uhl, Benedikt; Forster-Tonigold, Katrin; Bansmann, Joachim; Groß, Axel; Behm, R. Jürgen

2018-05-01

Ionic liquids (ILs) are considered as attractive electrolyte solvents in modern battery concepts such as Li-ion batteries. Here we present a comprehensive review of the results of previous model studies on the interaction of the battery relevant IL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMP]+[TFSI]-) with a series of structurally and chemically well-defined model electrode surfaces, which are increasingly complex and relevant for battery applications [Ag(111), Au(111), Cu(111), pristine and lithiated highly oriented pyrolytic graphite (HOPG), and rutile TiO2(110)]. Combining surface science techniques such as high resolution scanning tunneling microscopy and X-ray photoelectron spectroscopy for characterizing surface structure and chemical composition in deposited (sub-)monolayer adlayers with dispersion corrected density functional theory based calculations, this work aims at a molecular scale understanding of the fundamental processes at the electrode | electrolyte interface, which are crucial for the development of the so-called solid electrolyte interphase (SEI) layer in batteries. Performed under idealized conditions, in an ultrahigh vacuum environment, these model studies provide detailed insights on the structure formation in the adlayer, the substrate-adsorbate and adsorbate-adsorbate interactions responsible for this, and the tendency for chemically induced decomposition of the IL. To mimic the situation in an electrolyte, we also investigated the interaction of adsorbed IL (sub-)monolayers with coadsorbed lithium. Even at 80 K, postdeposited Li is found to react with the IL, leading to decomposition products such as LiF, Li3N, Li2S, LixSOy, and Li2O. In the absence of a [BMP]+[TFSI]- adlayer, it tends to adsorb, dissolve, or intercalate into the substrate (metals, HOPG) or to react with the substrate (TiO2) above a critical temperature, forming LiOx and Ti3+ species in the latter case. Finally, the formation of stable

Coverage Dependent Assembly of Anthraquinone on Au(111)

Science.gov (United States)

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.

Atomic structure of screw dislocations intersecting the Au(111) surface: A combined scanning tunneling microscopy and molecular dynamics study

DEFF Research Database (Denmark)

Engbæk, Jakob; Schiøtz, Jakob; Dahl-Madsen, Bjarke

2006-01-01

The atomic-scale structure of naturally occurring screw dislocations intersecting a Au(111) surface has been investigated both experimentally by scanning tunneling microscopy (STM) and theoretically using molecular dynamics (MD) simulations. The step profiles of 166 dislocations were measured using...... STM. Many of them exhibit noninteger step-height plateaus with different widths. Clear evidence was found for the existence of two different populations at the surface with distinct (narrowed or widened) partial-splitting widths. All findings are fully confirmed by the MD simulations. The MD...... simulations extend the STM-, i.e., surface-, investigation to the subsurface region. Due to this additional insight, we can explain the different partial-splitting widths as the result of the interaction between the partial dislocations and the surface....

Cysteine adsorption on the Au(111) surface and the electron transfer in configuration of a scanning tunneling microscope: A quantum-chemical approach

DEFF Research Database (Denmark)

Nazmutdinov, R.R.; Manyurov, I.R.; Zinkicheva, T.T.

2007-01-01

Adsorption of two forms, molecule and radical, of amino acid L-cysteine (Cys) on the Au-12 cluster that simulates the (111) face of single-crystal gold is studied in the framework of the density functional theory. Effects of solvation of adsorbed Cys particles and lateral interaction in a monolay...

Dynamics of decanethiol self-assembled monolayers on Au(111) studied by Scanning tunnelling microscopy

NARCIS (Netherlands)

Wu, Hairong; Sotthewes, Kai; Kumar, Avijit; Vancso, Gyula J.; Schön, Peter Manfred; Zandvliet, Henricus J.W.

2013-01-01

We investigated the dynamics of decanethiol self-assembled monolayers on Au(111) surfaces using time-resolved scanning tunneling microscopy at room temperature. The expected ordered phases (β, δ, χ*, and ) and a disordered phase (ε) were observed. Current–time traces with the feedback loop disabled

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

Energy Technology Data Exchange (ETDEWEB)

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

2007-11-12

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

Au nanoparticles on tryptophan-functionalized graphene for sensitive detection of dopamine

International Nuclear Information System (INIS)

Lian, Qianwen; Luo, Ai; An, Zhenzhen; Li, Zhuang; Guo, Yongyang; Zhang, Dongxia; Xue, Zhonghua; Zhou, Xibin; Lu, Xiaoquan

2015-01-01

Graphical abstract: - Highlights: • A novel AuNPs/Trp-GR composite was fabricated by directly electrochemical deposition. • The composite exhibited excellent electrocatalytic activity towards DA. • The proposed method was applied to real samples. - Abstract: A novel and uniform gold nanoparticles/tryptophan-functionalized graphene nanocomposite (AuNPs/Trp-GR) has been successfully fabricated by directly electrochemical depositing gold onto the surface of tryptophan-functionalized graphene (Trp-GR). The nanostructure of AuNPs/Trp-GR was characterized by using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). It was demonstrated that Au nanoparticles were well dispersed on the surface of Trp-GR which might attribute to the more binding sites provided by Trp-GR for the formation of Au nanoparticles. The electrocatalytic activity of the AuNPs/Trp-GR towards the dopamine (DA) was systematically investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Under optimum conditions, a wide and valuable linear range (0.5–411 μM), a low detection limit (0.056 μM, S/N = 3), good repeatability and stability were obtained for the determination of DA. Furthermore, the modified electrode was successfully applied to real samples analysis

Au nanoparticles on tryptophan-functionalized graphene for sensitive detection of dopamine

Energy Technology Data Exchange (ETDEWEB)

Lian, Qianwen; Luo, Ai; An, Zhenzhen; Li, Zhuang; Guo, Yongyang; Zhang, Dongxia [Key Laboratory of Bioelectrochemistry & Environmental Analysis of Gansu Province, College of Geography and Environment Science, Northwest Normal University, 730070, Lanzhou (China); Xue, Zhonghua [College of Chemistry and Chemical Engineering, Northwest Normal University, 730070, Lanzhou (China); Zhou, Xibin, E-mail: zhouxb@nwnu.edu.cn [Key Laboratory of Bioelectrochemistry & Environmental Analysis of Gansu Province, College of Geography and Environment Science, Northwest Normal University, 730070, Lanzhou (China); Lu, Xiaoquan, E-mail: Luxq@nwnu.edu.cn [College of Chemistry and Chemical Engineering, Northwest Normal University, 730070, Lanzhou (China)

2015-09-15

Graphical abstract: - Highlights: • A novel AuNPs/Trp-GR composite was fabricated by directly electrochemical deposition. • The composite exhibited excellent electrocatalytic activity towards DA. • The proposed method was applied to real samples. - Abstract: A novel and uniform gold nanoparticles/tryptophan-functionalized graphene nanocomposite (AuNPs/Trp-GR) has been successfully fabricated by directly electrochemical depositing gold onto the surface of tryptophan-functionalized graphene (Trp-GR). The nanostructure of AuNPs/Trp-GR was characterized by using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). It was demonstrated that Au nanoparticles were well dispersed on the surface of Trp-GR which might attribute to the more binding sites provided by Trp-GR for the formation of Au nanoparticles. The electrocatalytic activity of the AuNPs/Trp-GR towards the dopamine (DA) was systematically investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Under optimum conditions, a wide and valuable linear range (0.5–411 μM), a low detection limit (0.056 μM, S/N = 3), good repeatability and stability were obtained for the determination of DA. Furthermore, the modified electrode was successfully applied to real samples analysis.

Nitric oxide reduction and oxidation on stepped Pt[n(111)x(111)] electrodes

NARCIS (Netherlands)

Beltramo, G.L.; Koper, M.T.M.

2003-01-01

The structure sensitivity of the reduction and oxidation of saturated and subsaturated NO adlayers has been studied on a series of stepped Pt[n(111)×(111)] electrodes by cyclic and stripping voltammetry experiments in sulfuric and perchloric acid solution. In agreement with earlier experimental

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

Directory of Open Access Journals (Sweden)

Michael Paßens

2015-06-01

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

Electrochemical specific adsorption of halides on Cu 111, 100, and 211: A Density Functional Theory study

International Nuclear Information System (INIS)

McCrum, Ian T.; Akhade, Sneha A.; Janik, Michael J.

2015-01-01

The specific adsorption of ions onto electrode surfaces can affect electrocatalytic reactions. Density functional theory is used to investigate the specific adsorption of aqueous F − , Cl − , Br − , and I − onto Cu (111), (100), and (211) surfaces. The adsorption is increasingly favorable in the order of F − < Cl − < Br − < I − . The adsorption has a weak dependence on the surface facet, with adsorption most favorable on Cu (100) and least favorable on Cu (111). Potential ranges where specific adsorption would be expected on each facet are reported. The thermodynamics of bulk copper halide (CuX, CuX 2 ) formation are also investigated as a function of potential. CuX formation occurs at potentials slightly more positive of halide specific adsorption and of copper oxidation in aqueous electrolytes. Specifically adsorbed halides and bulk CuX may be present during a variety of electrochemical reactions carried out over a Cu electrode in halide containing electrolyte solutions

Magnetism of coherent Co and Ni thin films on Cu(111) and Au(111) substrates: An ab initio study

Energy Technology Data Exchange (ETDEWEB)

Zelený, Martin, E-mail: zeleny@fme.vutbr.cz; Dlouhý, Ivo

2017-02-15

We present an ab initio study of structural and magnetic properties of coherent Co and Ni thin films on Cu(111) and Au(111) substrates with thicknesses of up to 6 monolayers. All studied films on Cu(111) substrates prefer structures close their ground state (hcp for Co and fcc for Ni), whereas only the hcp stacking sequence has been found for both films on Au(111) substrates. All studied films exhibit instability of the first monolayer with respect to decomposition into 2-monolayer- or 3-monolayer-high islands, which is in agreement with experimental findings. All studied films are also ferromagnetic, nevertheless the Ni/Cu(111) films reduce their magnetic moments in the layer adjacent to the substrate due to a stronger Cu–Ni interaction at the interface. The magnetic anisotropy of a Co film does not depend on the film thickness: all the studied Co/Au(111) films exhibit a perpendicular magnetic anisotropy, whereas all the Co/Cu(111) films prefer in-plane magnetization. On the other hand, both Ni films change their preference for in-plane orientation of their easy axis to out-of-plane orientation at a critical thickness of 2 monolayers, however, the magnetic anisotropy energies for films thicker than 1 monolayer are smaller than 1 meV/Ni atom. These behaviors of magnetic anisotropy do not depend on the structure of the studied films. - Highlights: • All films exhibit instability of the first monolayer and prefer grow in islands. • The Cu–Ni interaction is responsible for reduced Ni magnetic moments in Ni/Cu(111) films. • The Co/Au(111) and Co/Cu(111) films show different orientations of magnetic anisotropy. • The Ni films exhibit in-plane magnetization only for single monolayer. • Behaviors of magnetic anisotropy do not depend on the structure of the studied films.

Adsorption and dehydrogenation of tetrahydroxybenzene on Cu(111)

DEFF Research Database (Denmark)

Bebensee, Fabian; Svane, K.; Bombis, Christian

2013-01-01

Adsorption of tetrahydroxybenzene (THB) on Cu(111) and Au(111) surfaces is studied using a combination of STM, XPS, and DFT. THB is deposited intact, but on Cu(111) it undergoes gradual dehydrogenation of the hydroxyl groups as a function of substrate temperature, yielding a pure dihydroxy......-benzoquinone phase at 370 K. Subtle changes to the adsorption structure upon dehydrogenation are explained from differences in molecule–surface bonding....

Monolayer Iron Carbide Films on Au(111) as a Fischer–Tropsch Model Catalyst

DEFF Research Database (Denmark)

Mannie, Gilbère; Lammich, Lutz; Li, Yong-Wang

2014-01-01

-temperature exposure of Fe islands gas to C2H4 deposited on the clean Au(111) surface results in partly converted Fe/FexCy islands. Multistep flash-heating treatment of the partly converted Fe/FexCy islands at 523 and 773 K results in pure highly crystalline FexCy islands with in-plane nearest-neighbor distances of 0...

Sensitive electrochemiluminescence biosensor based on Au-ITO hybrid bipolar electrode amplification system for cell surface protein detection.

Science.gov (United States)

Wu, Mei-Sheng; Yuan, Da-Jing; Xu, Jing-Juan; Chen, Hong-Yuan

2013-12-17

Here we developed a novel hybrid bipolar electrode (BPE)-electrochemiluminescence (ECL) biosensor based on hybrid bipolar electrode (BPE) for the measurement of cancer cell surface protein using ferrocence (Fc) labeled aptamer as signal recognition and amplification probe. According to the electric neutrality of BPE, the cathode of U-shaped ITO BPE was electrochemically deposited by Au nanoparticles (NPs) to enhance its conductivity and surface area, decrease the overpotential of O2 reduction, which would correspondingly increase the oxidation current of Ru(bpy)3(2+)/tripropylamine (TPA) on the anode of BPE and resulting a ∼4-fold enhancement of ECL intensity. Then a signal amplification strategy was designed by introducing Fc modified aptamer on the anode surface of BPE through hybridization for detecting the amount of mucin-1 on MCF-7 cells. The presence of Fc could not only inhibit the oxidation of Ru(bpy)3(2+) because of its lower oxidation potential, its oxidation product Fc(+) could also quench the ECL of Ru(bpy)3(2+)/TPA by efficient energy-transfer from the excited-state Ru(bpy)3(2+)* to Fc(+), making the ECL intensity greatly quenched. On the basis of the cathodic Au NPs induced ECL enhancing coupled with anodic Fc induced signal quenching amplification, the approach allowed detection of mucin-1 aptamer at a concentration down to 0.5 fM and was capable of detecting a minimum of 20 MCF-7 cells. Besides, the amount of mucin-1 on MCF-7 cells was calculated to be 9041 ± 388 molecules/cell. This approach therefore shows great promise in bioanalysis.

An efficient Monte Carlo algorithm for the fast equilibration and atomistic simulation of alkanethiol self-assembled monolayers on a Au(111) substrate.

Science.gov (United States)

Alexiadis, Orestis; Daoulas, Kostas Ch; Mavrantzas, Vlasis G

2008-01-31

A new Monte Carlo algorithm is presented for the simulation of atomistically detailed alkanethiol self-assembled monolayers (R-SH) on a Au(111) surface. Built on a set of simpler but also more complex (sometimes nonphysical) moves, the new algorithm is capable of efficiently driving all alkanethiol molecules to the Au(111) surface, thereby leading to full surface coverage, irrespective of the initial setup of the system. This circumvents a significant limitation of previous methods in which the simulations typically started from optimally packed structures on the substrate close to thermal equilibrium. Further, by considering an extended ensemble of configurations each one of which corresponds to a different value of the sulfur-sulfur repulsive core potential, sigmass, and by allowing for configurations to swap between systems characterized by different sigmass values, the new algorithm can adequately simulate model R-SH/Au(111) systems for values of sigmass ranging from 4.25 A corresponding to the Hautman-Klein molecular model (J. Chem. Phys. 1989, 91, 4994; 1990, 93, 7483) to 4.97 A corresponding to the Siepmann-McDonald model (Langmuir 1993, 9, 2351), and practically any chain length. Detailed results are presented quantifying the efficiency and robustness of the new method. Representative simulation data for the dependence of the structural and conformational properties of the formed monolayer on the details of the employed molecular model are reported and discussed; an investigation of the variation of molecular organization and ordering on the Au(111) substrate for three CH3-(CH2)n-SH/Au(111) systems with n=9, 15, and 21 is also included.

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

Energy Technology Data Exchange (ETDEWEB)

Kroes, Geert-Jan, E-mail: g.j.kroes@chem.leidenuniv.nl; Pavanello, Michele [Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (Netherlands); Blanco-Rey, María [Departamento de Física de Materiales, Facultad de Químicas UPV/EHU, Apartado 1072, 20080 Donostia-San Sebastián (Spain); Donostia International Physics Center, Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Alducin, Maite [Donostia International Physics Center, Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Centro de Física de Materiales, Centro Mixto CSIC-UPV/EHU, Paseo Manuel de Lardizabal 5, 20018 Donostia-San Sebastián (Spain); Auerbach, Daniel J. [Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (Netherlands); Max Planck Institute for Biophysical Chemistry, Göttingen (Germany); Institute for Physical Chemistry, Georg-August University of Göttingen, Göttingen (Germany)

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

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

Science.gov (United States)

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

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 in the

Surface reactivity of Ge[111] for organic functionalization by means of a radical-initiated reaction: A DFT study

Energy Technology Data Exchange (ETDEWEB)

Rubio-Pereda, Pamela, E-mail: rubio.pereda@gmail.com [Centro de Investigación Científica y de Educación Superior de Ensenada 3918, Código Postal 22860, Ensenada, Baja California (Mexico); Takeuchi, Noboru, E-mail: takeuchi@cnyn.unam.mx [Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Apartado Postal 14, Código Postal 22800, Ensenada, Baja California (Mexico)

2016-08-30

Highlights: • The surface reactivity of the Ge [111] surface is studied with DFT for the attachment of organic molecules by means of a radical-initiated reaction. • A hydrogen vacancy in the hydrogen terminated Ge [111] surface exhibits an accumulation of charge and electron pairing. • These characteristics make the hydrogen vacancy less reactive for the attachment of unsaturated organic molecules. • The adsorption of acetylene is probable to occur while the adsorption of ethylene and styrene is substantially less probable to occur. • The hydrogen terminated Ge [111] surface is found to be less reactive than its two-dimensional analogue, the hydrogen-terminated germanene. - Abstract: The study of interfacial chemistry at semiconductor surfaces has become an important area of research. Functionalities such as molecular recognition, biocompatibility of surfaces, and molecular computing, could be achieved by the combinations of organic chemistry with the semiconductor technology. One way to accomplish this goal is by means of organic functionalization of semiconductor surfaces such as the bulk-terminated germanium surfaces, more specifically the Ge[111]. In this work, we theoretically study, by applying density functional theory, the surface reactivity of the bulk-terminated Ge[111] surface for organic functionalization by means of a radical-initiated reaction of unsaturated molecules such as acetylene, ethylene and styrene with a hydrogen vacancy on a previously hydrogen-terminated Ge[111] surface. Results derived from this work are compared with those obtained in our previous calculations on the germanene surface, following the same chemical route. Our calculations show an accumulation of electronic charge at the H-vacancy having as a result electron pairing due to strong lattice-electron coupling and therefore a diminished surface reactivity. Calculation of the transition states for acetylene and ethylene indicates that the surface reactivity of the

Deformation of Ag clusters deposited on Au(111) - Experiment and molecular dynamics

Energy Technology Data Exchange (ETDEWEB)

Miroslawski, Natalie; Groenhagen, Niklas; Hoevel, Heinz [TU Dortmund, Experimentelle Physik I (Germany); Issendorff, Bernd von [Universitaet Freiburg, Fakultaet Physik (Germany); Jaervi, Tommi [Fraunhofer Institut fuer Werkstoffmechanik, Freiburg (Germany); Moseler, Michael [Universitaet Freiburg, Fakultaet Physik (Germany); Fraunhofer Institut fuer Werkstoffmechanik, Freiburg (Germany); Freiburger Materialforschungszentrum (Germany)

2011-07-01

Mass selected clusters from Ag{sup +}{sub 55} to Ag{sup +}{sub 147{+-}}{sub 2} were deposited with different deposition energies at 77 K on Au(111) and imaged with STM at 77 K. We observed a deformation of the cluster shape due to the strong metallic interaction between the cluster and the substrate. The clusters became epitaxial and developed a structure composed of several Ag monolayers. The number of these monolayers depends on the number of atoms in the cluster and the deposition energy. The larger the cluster mass the more monolayers the cluster develops on Au(111) and the larger the deposition energy the fewer monolayers occur. These results were verified by molecular dynamic simulations. Additionally the behaviour of Ag{sub N} clusters on Au(111) after different annealing steps was investigated.

First-principles study of surface plasmons on Ag(111) and H/Ag(111)

DEFF Research Database (Denmark)

Yan, Jun; Jacobsen, Karsten Wedel; Thygesen, Kristian Sommer

2011-01-01

Linear-response time-dependent density functional theory is used to investigate the relation between molecular bonding and surface plasmons for the model system H/Ag(111). We employ an orbital-dependent exchange-correlation functional to obtain a correct description of the Ag 3d band, which...... is crucial to avoid overscreening the plasmon by the s-d interband transitions. For the clean surface, this approach reproduces the experimental plasmon energies and dispersion to within 0.15 eV. Adsorption of hydrogen shifts and damps the Ag(111) surface plasmon and induces a new peak in the loss function...... at 0.6 eV below the Ag(111) plasmon peak. This feature originates from interband transitions between states located on the hydrogen atoms and states on the Ag surface atoms....

Broader energy distribution of CO adsorbed at polycrystalline Pt electrode in comparison with that at Pt(111) electrode in H_2SO_4 solution confirmed by potential dependent IR/visible double resonance sum frequency generation spectroscopy

International Nuclear Information System (INIS)

Yang, Shuo; Noguchi, Hidenori; Uosaki, Kohei

2017-01-01

Highlights: • Electrochemical SFG spectroscopy is an efficient in situ probe of electronic structure at electrochemical interface. • Electrooxidation performances of CO adsorbed on polycrystalline Pt and Pt(111) electrodes were compared. • The enhanced SFG signal of CO on Pt electrodes was observed due to a vibrational-electronic double resonance effect. • The broader energy distribution of 5sa state of CO on polycrystalline Pt than on Pt(111) is proved by SFG results. - Abstract: Electrochemical cyclic voltammetry and potential dependent double resonance sum frequency generation (DR-SFG) spectroscopy were performed on CO adsorbed on polycrystalline Pt and Pt(111) electrodes in H_2SO_4 solution to examine the effect of substrate on the electronic structure of CO. The dependence of SFG intensity on potential and visible energy for atop CO band was observed on both polycrystalline and single crystalline Pt electrodes. Enhancement of the SFG intensity was determined to be a direct result of a surface electronic resonance of the visible/SF light with the electronic transition from Fermi level of Pt to the 5σ_a anti-bonding state of adsorbed CO, in agreement with previous results. Interestingly, when compared to the Pt(111) electrode, the distribution width of the intensity enhancement region on polycrystalline Pt is broader than on Pt(111). This suggests that the energy distribution of the 5σ_a state of CO on polycrystalline Pt surface is broader than that on Pt(111) due to the complex surface structure of the polycrystalline Pt electrode.

Chemical vapour deposition of graphene on Nk(111) and Co(0001) and intercalation with Au to study Dirac Cone Formation and Rashba splitting

Energy Technology Data Exchange (ETDEWEB)

Sanchez-Barriga, J.; Vescovo, E.; Varykhalov, A.; Scholz, M.R.; Rader, O.; Marchenko, D.; Rybkin, A.

2010-01-01

We show in detail monitoring by photoelectron spectroscopy how graphene can be grown by chemical vapor deposition on the transition-metal surfaces Ni(111) and Co(0001) and intercalated by a monoatomic layer of Au. For both systems, a linear E(k) dispersion of massless Dirac fermions appears in the graphene {pi}-band in the vicinity of the Fermi energy. In order to study ferromagnetism and spin-orbit effects by spin- and angle-resolved photoelectron spectroscopy, the sample must be magnetized in remanence. To this end, a W(110) substrate is prepared, its cleanliness verified by photoemission from W(110) surface states and surface core levels, and epitaxial Ni(111) and Co(0001) thin films are grown on top. Spin-resolved photoemission from the {pi}-band shows that the ferromagnetic polarization of graphene/Ni(111) and graphene/Co(0001) is negligible and that graphene on Ni(111) is after intercalation of Au spin-orbit split by the Rashba effect.

Influence of Au Nanoparticle Shape on Au@Cu2O Heterostructures

Directory of Open Access Journals (Sweden)

Jie Zhu

2015-01-01

Full Text Available Synthesis of metal-semiconductor heterostructures may allow the combination of function of the corresponding components and/or the enhanced performance resulting from the interactions between all the components. In this paper, Au@Cu2O core-shell heterostructures are prepared by a seed-growth method, using different-shaped Au nanocrystals as the seeds such as nanorods, octahedra, decahedra, dots, and nanocubes. The results revealed that the final structure of Au@Cu2O was greatly influenced by the shape of the seeds used. Exposure of Cu2O{111} and Cu2O{001} favored when the overgrowth happened on Au{111} and Au{001} surface, respectively. The size of the product can also be tuned by the amount of the seeds. The results reported here provide a thinking clue to modulate the shape and size of core-shell nanocrystals, which is useful in developing new materials with desired performance.

Electrodéposition et la caractérisation de nanofilms palladium sur Au (111) pour le stockage d'hydrogène Electro-deposition and characterization of palladium nanofilms on Au (111) for hydrogen storage

OpenAIRE

Wang , Liang

2012-01-01

This thesis focused on electro-deposition, characterization andhydrogen strorage of ultrathin palladium film over Au(111). Theelectrochemical characterization of the nanofilms in sulphuric mediumshows well-defined features evolving with the deposit thickness. Wecould assign each peak to a specific reaction, in agreement with thegrowth mechanisms revealed by in situ SXRD measurements. Thepseudomorphic growth of the 1st layer firstly undergoes an adsorptionstep, followed by nucleation and growt...

The nonenzyme ethanol sensor based on pt nps and fe/sub 3/O/sub 4/ mnps modified au electrode

International Nuclear Information System (INIS)

Wan, J.; Ma, X.; Yin, G.

2013-01-01

The none enzyme ethanol sensor was prepared using Pt nanoparticles (NPs) and Fe/sub 3/O/sub 4/ magnetic nanoparticles (MNPs) modified Au electrode. Pt NPs were deposited on the gold plated electrode through the method of potentiostatic deposition. Fe/sub 3/O/sub 4/ magnetic nanoparticles were added to the surface of Pt NPs modified Au electrode to obtain the Au/Pt/ Fe/sub 3/O/sub 4/ MNPs electrode. The as-prepared Au/Pt/Fe/sub 3/O/sub 4/ MNPs electrode was used for the detection of liquid ethanol without using enzyme. Cyclic voltammetry and differential pulse voltammetry were used to study the behavior of ethanol electro-catalytic oxidation on Pt/Au/Fe/sub 3/O/sub 4/ electrode. It was found that Pt NPs played strong catalytic oxidation role of ethanol with the presence of Fe/sub 3/O/sub 4/ MNPs. The linear range of Au/Pt/Fe/sub 3/O/sub 4/ MNPs electrode for the detection of ethanol was of 2 x 10 /sup -5/ 1.1 x 10/sup -4/ mol L/sup -1/ and the detection limit was of 3.2 x 10/sup -6/ mol L/sup -5/ when signal to noise ratio was 3sigma. The sensibility of the sensor is 420.4 microA mmol/sup -1/ /sup -2cm/. The simple method provided an effective means for fabricating the novel sensors. (author)

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

Science.gov (United States)

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.

In situ diffraction studies of electrode surface structure during gold electrodeposition

International Nuclear Information System (INIS)

Magnussen, O.M.; Krug, K.; Ayyad, A.H.; Stettner, J.

2008-01-01

Surface X-ray scattering (SXS) in transmission geometry provides a valuable tool for in situ structural studies of electrochemical interfaces under reaction conditions, as illustrated here for homoepitaxial electrodeposition on Au(1 0 0) and Au(1 1 1) electrodes. Employing diffusion-limited deposition conditions to separate the effects of potential and deposition rate, a mutual interaction between the interface structure and the growth behavior is found. Time-dependent SXS measurements during Au(1 0 0) homoepitaxy show with decreasing potential transitions from step flow to layer-by-layer growth, then to multilayer growth, and finally back to layer-by-layer growth. This complex growth behavior can be explained within the framework of kinetic growth theory by the effect of potential, Cl adsorbates and the Au surface structure, specifically the presence of the surface reconstruction, on the Au surface mobility. Conversely, the electrodeposition process influences the structure of the reconstructed Au surface, as illustrated for Au(1 1 1), where a significant deposition-induced compression of the Au surface layer as compared to Au(1 1 1) surfaces under ultrahigh vacuum conditions or in Au-free electrolyte is found. This compression increases towards more negative potentials, which may be explained by a release of potential-induced surface stress

Ab initio simulations of scanning-tunneling-microscope images with embedding techniques and application to C58-dimers on Au(111).

Science.gov (United States)

Wilhelm, Jan; Walz, Michael; Stendel, Melanie; Bagrets, Alexei; Evers, Ferdinand

2013-05-14

We present a modification of the standard electron transport methodology based on the (non-equilibrium) Green's function formalism to efficiently simulate STM-images. The novel feature of this method is that it employs an effective embedding technique that allows us to extrapolate properties of metal substrates with adsorbed molecules from quantum-chemical cluster calculations. To illustrate the potential of this approach, we present an application to STM-images of C58-dimers immobilized on Au(111)-surfaces that is motivated by recent experiments.

Synthesis of Epitaxial Single-Layer MoS2 on Au(111).

Science.gov (United States)

Grønborg, Signe S; Ulstrup, Søren; Bianchi, Marco; Dendzik, Maciej; Sanders, Charlotte E; Lauritsen, Jeppe V; Hofmann, Philip; Miwa, Jill A

2015-09-08

We present a method for synthesizing large area epitaxial single-layer MoS2 on the Au(111) surface in ultrahigh vacuum. Using scanning tunneling microscopy and low energy electron diffraction, the evolution of the growth is followed from nanoscale single-layer MoS2 islands to a continuous MoS2 layer. An exceptionally good control over the MoS2 coverage is maintained using an approach based on cycles of Mo evaporation and sulfurization to first nucleate the MoS2 nanoislands and then gradually increase their size. During this growth process the native herringbone reconstruction of Au(111) is lifted as shown by low energy electron diffraction measurements. Within the MoS2 islands, we identify domains rotated by 60° that lead to atomically sharp line defects at domain boundaries. As the MoS2 coverage approaches the limit of a complete single layer, the formation of bilayer MoS2 islands is initiated. Angle-resolved photoemission spectroscopy measurements of both single and bilayer MoS2 samples show a dramatic change in their band structure around the center of the Brillouin zone. Brief exposure to air after removing the MoS2 layer from vacuum is not found to affect its quality.

Synthesis and electronic properties of chemically functionalized graphene on metal surfaces

International Nuclear Information System (INIS)

Grüneis, Alexander

2013-01-01

A review on the electronic properties, growth and functionalization of graphene on metals is presented. Starting from the derivation of the electronic properties of an isolated graphene layer using the nearest neighbor tight-binding (TB) approximation for π and σ electrons, the TB model is then extended to third-nearest neighbors and interlayer coupling. The latter is relevant to few-layer graphene and graphite. Next, the conditions under which epitaxial graphene can be obtained by chemical vapor deposition are reviewed with a particular emphasis on the Ni(111) surface. Regarding functionalization, I first discuss the intercalation of monolayer Au into the graphene/Ni(111) interface, which renders graphene quasi-free-standing. The Au intercalated quasi-free-standing graphene is then the basis for chemical functionalization. Functionalization of graphene is classified into covalent, ionic and substitutional functionalization. As archetypical examples for these three possibilities I discuss covalent functionalization by hydrogen, ionic functionalization by alkali metals and substitutional functionalization by nitrogen heteroatoms.

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

International Nuclear Information System (INIS)

Alvarez, Lucia; Caillard, Renaud; MartIn-Gago, Jose A; Mendez, Javier; Pelaez, Samuel; Serena, Pedro A

2010-01-01

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.

Efficient CH3NH3PbI3 perovskite/fullerene planar heterojunction hybrid solar cells with oxidized Ni/Au/Cu transparent electrode

Science.gov (United States)

Lai, Wei-Chih; Lin, Kun-Wei; Guo, Tzung-Fang; Chen, Peter; Liao, Yuan-Yu

2018-02-01

We demonstrated the performance of inverted CH3NH3PbI3 perovskite-based solar cells (SCs) with a thermally oxidized nickel/gold/copper (Ni/Au/Cu) trilayer transparent electrode. Oxidized Ni/Au/Cu is a high transparent layer and has less resistance than the oxidized Ni/Au layer. Like the oxidized Ni/Au layer, oxidized Ni and Cu in oxidized Ni/Au/Cu could perform as a hole transport layer of the perovskite-based SCs. It leads to improved perovskite SC performance on an open circuit voltage of 1.01 V, a short circuit current density of 14.36 mA/cm2, a fill factor of 76.7%, and a power conversion efficiency (η%) of 11.1%. The η% of perovskite SCs with oxidized Ni (10 nm)/Au (6 nm)/Cu (1 nm) improved by approximately 10% compared with that of perovskite SCs with oxidized Ni/Au.

Molecular assembly and electro polymerization of 3,4-ethylenedioxy thiophene on Au(100) single crystal electrode using in-situ electrochemical scanning tunneling microscopy

International Nuclear Information System (INIS)

Garcia, Jonyl L.; Tongol, Bernard John V.; ShuehLin Yau

2012-01-01

Electrochemical scanning tunneling microscopy (Ec-STM) is a powerful technique that can provide molecular-level information regarding electrode surface processes in-situ in electrolyte solvent under ambient conditions. In this study, the adsorption and electro polymerization of an industrially important conducting polymer precursor, 3,4-ethylenedioxy thiophene (EDOT), on Au (100) single crystal was probed using Ec-STM. The Au (100) single crystal electrode substrate used for this study was fabricated using the well-known Clavilier's flame melting procedure. Cyclic voltammetry (CV) was used along with Ec-STM to characterize the bare, EDOT-modified, and poly(EDOT)-modified Au (100) single crystal electrode. Time-dependent Ec-STM imaging at 0.550 V showed the formation of an EDOT self-assembled monolayer through 2-D surface dillusion. The resulting EDOT molecular assembly on Au (100) single crystal electrode was found to fit in a 4√2χ3√2 unit cell. Difference in apparent corrugation between molecular rows was attributed to different angular orientation with respect to the substrate. The electro polymerization of EDOT on Au (100) single crystal electrode was done by potentiostatic and potentiodynamic methods. Both methods suggested a solution-process mechanism for EDOT electro polymerization. (author)

Methanol oxidation on stepped Pt[n(111) x (110)] electrodes: a chronoamperometric study

NARCIS (Netherlands)

Housmans, T.H.M.; Koper, M.T.M.

2003-01-01

The methanol oxidation reaction has been studied on Pt[n(111) × (110)]-type electrodes in a 0.5 M sulfuric acid and 0.025 M methanol solution, using cyclic voltammetry and chronoamperometry. The voltammetric behavior of methanol on the three electrodes under investigation [Pt(111), Pt(554), and

Novel surface diffusion characteristics for a robust pentacene derivative on Au(1 1 1) surfaces

Science.gov (United States)

Miller, Ryan A.; Larson, Amanda; Pohl, Karsten

2017-06-01

Molecular dynamics simulations have been performed in both the ab initio and classical mechanics frameworks of 5,6,7-trithiapentacene-13-one (TTPO) molecules on flat Au(1 1 1) surfaces. Results show new surface diffusion characteristics including a strong preference for the molecule to align its long axis parallel to the sixfold Au(1 1 1) symmetry directions and subsequently diffuse along these close-packed directions, and a calculated activation energy for diffusion of 0.142 eV, about four times larger than that for pure pentacene on Au. The temperature-dependent diffusion coefficients were calculated to help quantify the molecular mobility during the experimentally observed process of forming self-assembled monolayers on gold electrodes.

Electrolysis of water on (oxidized) metal surfaces

DEFF Research Database (Denmark)

Rossmeisl, Jan; Logadottir, Ashildur; Nørskov, Jens Kehlet

2005-01-01

Density functional theory calculations are used as the basis for an analysis of the electrochemical process, where by water is split to form molecular oxygen and hydrogen. We develop a method for obtaining the thermochemistry of the electrochemical water splitting process as a function of the bias...... directly from the electronic structure calculations. We consider electrodes of Pt(111) and Au(111) in detail and then discuss trends for a series of different metals. We show that the difficult step in the water splitting process is the formation of superoxy-type (OOH) species on the surface...... by the splitting of a water molecule on top an adsorbed oxygen atom. One conclusion is that this is only possible on metal surfaces that are (partly) oxidized. We show that the binding energies of the different intermediates are linearly correlated for a number of metals. In a simple analysis, where the linear...

Theoretical studies of the work functions of Pd-based bimetallic surfaces

International Nuclear Information System (INIS)

Ding, Zhao-Bin; Wu, Feng; Wang, Yue-Chao; Jiang, Hong

2015-01-01

Work functions of Pd-based bimetallic surfaces, including mainly M/Pd(111), Pd/M, and Pd/M/Pd(111) (M = 4d transition metals, Cu, Au, and Pt), are studied using density functional theory. We find that the work function of these bimetallic surfaces is significantly different from that of parent metals. Careful analysis based on Bader charges and electron density difference indicates that the variation of the work function in bimetallic surfaces can be mainly attributed to two factors: (1) charge transfer between the two different metals as a result of their different intrinsic electronegativity, and (2) the charge redistribution induced by chemical bonding between the top two layers. The first factor can be related to the contact potential, i.e., the work function difference between two metals in direct contact, and the second factor can be well characterized by the change in the charge spilling out into vacuum. We also find that the variation in the work functions of Pd/M/Pd(111) surfaces correlates very well with the variation of the d-band center of the surface Pd atom. The findings in this work can be used to provide general guidelines to design new bimetallic surfaces with desired electronic properties

Long-Range Interfacial Electrochemical Electron Transfer of Pseudomonas aeruginosa Azurin-Gold Nanoparticle Hybrid Systems

DEFF Research Database (Denmark)

Jensen, Palle Skovhus; Chi, Qijin; Zhang, Jingdong

2009-01-01

We have prepared a "hybrid" of the blue copper protein azurin (Pseudomonas aeruginosa) and a 3 nm gold nanoparticle (AuNP). The AuNP/azurin hybrid was assembled on a Au(111)-electrode surface in a two-step process. The AuNP was first attached to the Au(111) electrode via Au-S chemisorption of a 4...

Characterization of self-assembled electrodes based on Au-Pt nanoparticles for PEMFC application

Energy Technology Data Exchange (ETDEWEB)

Valenzuela, E. [Univ. Politecnica de Chiapas (Mexico). Energia y Sustentabilidad; Sebastian, P.J.; Gamboa, S.A.; Joseph, S. [Univ. Nacional Autonoma de Mexico, Morelos (Mexico). Centrode Investigacion en Energia; Pal, U. [Univ. Autonoma de Puebla, Pue (Mexico). Inst. de Fisica; Gonzalez, I. [Univ. Autonoma Metropolitana, Mexico City (Mexico). Dept. de Quimica

2010-07-01

This paper described the synthesis and characterization of gold (Au), platinum (Pt) and Au-Pt nanoparticles impregnated on a Nafion membrane in a proton exchange membrane fuel cell (PEMFC). The aim of the study was to fabricate the membrane electrode assembly (MEA) by depositing the nanoparticles on the membrane using an immersion technique. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to study the deposition process. Electrochemical impedance spectroscopy (EIS) was used to study the membrane proton conduction process. An elemental mapping analysis was performed in order to study the location of the Au and Pt in the self-assemblies. Results of the study showed that the particles deposited on the Nafion had good stability and a homogenous distribution along the membrane surface. The particles showed a direct relation in size and location with the hydrophilic and hydrophobic distribution phases of the membrane. The main membrane resistance was located between the membrane and the electrolyte. The self-assembled electrodes demonstrated a good performance at standard conditions. 33 refs., 4 tabs., 11 figs.

Electronic structure of low work function electrodes modified by C{sub 16}H{sub 33}SH

Energy Technology Data Exchange (ETDEWEB)

Lee, Hyunbok [Department of Polymer Science and Engineering, University of Massachusetts, Amherst, MA, 01003 (United States); Cho, Sang Wan, E-mail: dio8027@yonsei.ac.kr [Department of Physics, Yonsei University, 1 Yonseidae-gil, Wonju-si, Gangwon-do, 220-710 (Korea, Republic of); Park, Sang Han; Cho, Mann-Ho; Yi, Yeonjin [Institute of Physics and Applied Physics, Yonsei University, 50 Yonsei-ro, Seodaemoon-Gu, Seoul, 120-749 (Korea, Republic of)

2014-10-15

Highlights: • The electronic structure of pentacene/C{sub 16}H{sub 33}SH/Au is investigated. • The work function of Au is significantly decreased with C{sub 16}H{sub 33}SH treatment. • The reduced work function is attributed to its permanent dipole moment. - Abstract: Organic and printed electronics technologies require electrodes with low work functions to facilitate the transport of electrons in and out of various optoelectronic devices. We show that the surface modifier of 1-hexadecanethiol reduces the work function of conductors using in situ ultraviolet photoemission spectroscopy, and we combine experimental and theoretical methods to investigate the origin of the work function changes. The interfacial electronic structures of pentacene/1-hexadecanethiol/Au were investigated via in situ ultraviolet photoemission spectroscopy and X-ray photoemission spectroscopy in order to understand the change in the carrier injection barrier and chemical reactions upon surface modification. Theoretical calculations using density functional theory were also performed to understand the charge distribution of 1-hexadecanethiol, which affects the reduction of the work function. The 1-hexadecanethiol surface modifier is processed in air from solution, providing an appealing alternative to chemically-reactive low-work-function metals.

A novel electrochemical sensor based on magneto Au nanoparticles/carbon paste electrode for voltammetric determination of acetaminophen in real samples

Energy Technology Data Exchange (ETDEWEB)

Haghshenas, Esmaeel; Madrakian, Tayyebeh, E-mail: madrakian@basu.ac.ir; Afkhami, Abbas

2015-12-01

An electrochemical magneto Au nanoparticles/carbon paste electrodes (MAuNP/CPE) which is used for the determination of acetaminophen (AC) in real samples was developed. Initially, Au nanoparticles were immobilized at the surface of Fe{sub 3}O{sub 4} (AuNPs@Fe{sub 3}O{sub 4}), which was used as a sorbent for capturing AC molecules. After adding AuNPs@Fe{sub 3}O{sub 4} to the AC solution and stirring for 20 min, the AuNPs@Fe{sub 3}O{sub 4} was gathered on the magneto electrode based on its magnetic field. The AC molecules which became adsorbed at AuNPs@Fe{sub 3}O{sub 4} were analyzed by differential pulse voltammetry (DPV). For characterization and investigation of the performance of AuNPs@Fe{sub 3}O{sub 4} and MAuNPs/CPE, various methods, including scanning electron microscopy, X-ray diffraction, UV–Vis spectroscopy, electrochemical impedance spectroscopy, cyclic voltammetry and DPV were used. Under the optimized conditions, the anodic peak current was linear to the concentration of AC in the range of 0.1 to 70.0 μmol L{sup −1} with the detection limit of 4.5 × 10{sup −2} μmol L{sup −1}. This method was also successfully used to detect the concentration of AC in pharmaceutical formulations and human serum samples. In addition, the proposed magneto sensor exhibited good reproducibility, long-term stability and fast current response. - Highlights: • Magneto Au nanoparticle/carbon paste electrode was fabricated. • Au nanoparticles were immobilized at the surface of Fe{sub 3}O{sub 4} (AuNPs@Fe{sub 3}O{sub 4}). • It is the first time AuNPs@Fe{sub 3}O{sub 4} and magneto electrode are used for the determination of AC. • The proposed sensor showed a wide linear range, low detection limit, and high sensitivity. • This sensor is also used for the determination of AC in real samples.

Sputter deposition on gas diffusion electrodes of Pt-Au nanoclusters for methanol oxidation

Energy Technology Data Exchange (ETDEWEB)

Giorgi, L.; Giorgi, R.; Gagliardi, S.; Serra, E. [ENEA Casaccia Research Center, Rome (Italy). Physics Technologies and New Materials; Alvisi, M.; Signore, M.A. [ENEA Brindisi Research Center, Brindisi (Italy). Physics Technologies and New Materials

2008-07-01

Polymer electrolyte fuel cells (PEFCs) are suited for use in commercial electrical vehicle and electric power applications. The gas diffusion electrodes of PEFCs are catalyzed by the deposition of platinum (Pt) nanoparticles on carbon powder. The particles must be localized on the electrode surface in order to achieve high electrocatalyst utilization. This study discussed a method of preparing PEFC electrodes using sputter deposition of a Pt-gold (Au) alloy nanoparticles on carbon powders. The method was designed to improve electrode performance and catalyst utilization. The nano-sized alloy clusters were deposited on a gas diffusion electrode at room temperature. The deposits were then characterized using field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) in order to examine the effect of the deposition technique on the nano-morphology and electrocatalytic performance of the electrode. Results of the study showed that the technique can be used in the large-scale manufacture of fuel cell electrodes. 3 refs., 1 fig.

Surface functional groups in capacitive deionization with porous carbon electrodes

Science.gov (United States)

Hemmatifar, Ali; Oyarzun, Diego I.; Palko, James W.; Hawks, Steven A.; Stadermann, Michael; Santiago, Juan G.; Stanford Microfluidics Lab Team; Lawrence Livermore National Lab Team

2017-11-01

Capacitive deionization (CDI) is a promising technology for removal of toxic ions and salt from water. In CDI, an applied potential of about 1 V to pairs of porous electrodes (e.g. activated carbon) induces ion electromigration and electrostatic adsorption at electrode surfaces. Immobile surface functional groups play a critical role in the type and capacity of ion adsorption, and this can dramatically change desalination performance. We here use models and experiments to study weak electrolyte surface groups which protonate and/or depropotante based on their acid/base dissociation constants and local pore pH. Net chemical surface charge and differential capacitance can thus vary during CDI operation. In this work, we present a CDI model based on weak electrolyte acid/base equilibria theory. Our model incorporates preferential cation (anion) adsorption for activated carbon with acidic (basic) surface groups. We validated our model with experiments on custom built CDI cells with a variety of functionalizations. To this end, we varied electrolyte pH and measured adsorption of individual anionic and cationic ions using inductively coupled plasma mass spectrometry (ICP-MS) and ion chromatography (IC) techniques. Our model shows good agreement with experiments and provides a framework useful in the design of CDI control schemes.

Antibacterial Au nanostructured surfaces

Science.gov (United States)

Wu, Songmei; Zuber, Flavia; Brugger, Juergen; Maniura-Weber, Katharina; Ren, Qun

2016-01-01

We present here a technological platform for engineering Au nanotopographies by templated electrodeposition on antibacterial surfaces. Three different types of nanostructures were fabricated: nanopillars, nanorings and nanonuggets. The nanopillars are the basic structures and are 50 nm in diameter and 100 nm in height. Particular arrangement of the nanopillars in various geometries formed nanorings and nanonuggets. Flat surfaces, rough substrate surfaces, and various nanostructured surfaces were compared for their abilities to attach and kill bacterial cells. Methicillin-resistant Staphylococcus aureus, a Gram-positive bacterial strain responsible for many infections in health care system, was used as the model bacterial strain. It was found that all the Au nanostructures, regardless their shapes, exhibited similar excellent antibacterial properties. A comparison of live cells attached to nanotopographic surfaces showed that the number of live S. aureus cells was flat and rough reference surfaces. Our micro/nanofabrication process is a scalable approach based on cost-efficient self-organization and provides potential for further developing functional surfaces to study the behavior of microbes on nanoscale topographies.We present here a technological platform for engineering Au nanotopographies by templated electrodeposition on antibacterial surfaces. Three different types of nanostructures were fabricated: nanopillars, nanorings and nanonuggets. The nanopillars are the basic structures and are 50 nm in diameter and 100 nm in height. Particular arrangement of the nanopillars in various geometries formed nanorings and nanonuggets. Flat surfaces, rough substrate surfaces, and various nanostructured surfaces were compared for their abilities to attach and kill bacterial cells. Methicillin-resistant Staphylococcus aureus, a Gram-positive bacterial strain responsible for many infections in health care system, was used as the model bacterial strain. It was found that all

Dehydrogenation of benzene on Pt(111) surface

Science.gov (United States)

Gao, W.; Zheng, W. T.; Jiang, Q.

2008-10-01

The dehydrogenation of benzene on Pt(111) surface is studied by ab initio density functional theory. The minimum energy pathways for benzene dehydrogenation are found with the nudge elastic band method including several factors of the associated barriers, reactive energies, intermediates, and transient states. The results show that there are two possible parallel minimum energy pathways on the Pt(111) surface. Moreover, the tilting angle of the H atom in benzene can be taken as an index for the actual barrier of dehydrogenation. In addition, the properties of dehydrogenation radicals on the Pt(111) surface are explored through their adsorption energy, adsorption geometry, and electronic structure on the surface. The vibrational frequencies of the dehydrogenation radicals derived from the calculations are in agreement with literature data.

Functionalized Nanoporous Track Etched {beta}-PVDF Membrane Electrodes for Lead (II) Determination by Square Wave Anodic Stripping Voltammetry

Energy Technology Data Exchange (ETDEWEB)

Bessbousse, H [Laboratoire des Solides Irradies, CEA-CNRS-Ecole Polytechnique, 91128 Palaiseau (France); Nadhakumar, I [School of Chemistry, University of Southampton, University Road, Southampton S017 1BJ (United Kingdom); Decker, M; Clochard, M -C; Wade, T L [Laboratoire des Solides Irradies, CEA-CNRS-Ecole Polytechnique, 91128 Palaiseau (France); Barsbay, M [Hacettepe University, Department of Chemistry, Polymer Chemistry Division, 06800 Beytepe Ankara (Turkey)

2012-09-15

Track etched functionalized nanoporous {beta}-PVDF membrane electrodes, or functionalized membrane electrodes (FME), are thin-layer cells made from poly(acrylic acid) (PAA) functionalized nanoporous {beta}-poly(vinylidene fluoride) ({beta}-PVDF) membranes with thin Au films sputtered on each side as electrodes. The Au film is thin enough that the pores of the membranes are not completely covered. The PAA functionalization is specifically localised in the walls of the nanoporous {beta}-PVDF membrane by grafting. The PAA is a cation exchange polymer that adsorbs metal ions, such as Pb{sup 2+}, from aqueous solutions concentrating the ions into the membrane. After a time the FME is transferred to an electrochemical cell for analysis. A negative potential is applied to the Au film of the FME for a set time to reduce the adsorbed ions onto the Au film working electrode. The other metalized side of the FME functions as a counter electrode. Finally, square-wave anodic stripping voltammetry (SW-ASV) is performed on the FME to determine the metal ion concentrations in the original solution. The calibration curve of charge versus log concentration has a Temkin isotherm form. The FME membranes are 9 {mu}m thick and have 40 nm diameter pores with a density of 10{sup 10} pores/cm{sup 2}. This high pore density provides a large capacity for ion adsorption. Au ingress in the pores during sputtering forms a random array of nanoelectrodes. Like surface modified electrodes for adsorptive stripping voltammetry, the pre-concentration step for the FME is performed at open circuit. The zero current intercept of the calibration for Pb{sup 2+} is 0.13 ppb ({mu}g/L) and a detection limit of 0.050 ppb based on 3S/N from blank measurements. Voltammetry (CV) and chronoapmerometry (CA) were used to characterize the system. The apparent diffusion coefficient (D) for Pb{sup 2+} in the PAA functionalized pores was determined to be 2.44 x 10{sup -7} cm{sup 2}/s and the partition coefficient (p

Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)-electrodes: Effects of the heteroatomic junction on the reaction paths

Science.gov (United States)

Schulte, E.; Belletti, G.; Arce, M.; Quaino, P.

2018-05-01

The seek for materials to enhance the oxygen reduction reaction (orr) rate is a highly relevant topic due to its implication in fuel cell devices. Herein, the orr on bimetallic electrocatalysts based on Au-M (M = Pt, Pd) has been studied computationally, by performing density functional theory calculations. Bimetallic (1 0 0) electrode surfaces with two different Au:M ratios were proposed, and two possible pathways, associative and dissociative, were considered for the orr. Changes in the electronic properties of these materials with respect to the pure metals were acknowledged to gain understanding in the overall reactivity trend. The effect of the bimetallic junction on the stability of the intermediates O2 and OOH was also evaluated by means of geometrical and energetic parameters; being the intermediates preferably adsorbed on Pt/Pd atoms, but presenting in some cases higher adsorption energies compared with bare metals. Finally, the kinetics of the Osbnd O bond breaking in O2∗ and OOH∗ adsorbed intermediates in the bimetallic materials and the influence of the Au-M junction were studied by means of the nudge elastic-band method. A barrierless process for the scission of O2∗ was found in Au-M for the higher M ratios. Surprisingly, for Au-M with lower M ratios, the barriers were much lower than for pure Au surfaces, suggesting a highly reactive surface towards the orr. The Osbnd O scission of the OOH∗ was found to be a barrierless process in Ausbnd Pt systems and nearly barrierless in all Ausbnd Pd systems, implying that the reduction ofO2 in these systems proceeds via the full reduction of O2 to H2O , avoiding H2O2 formation.

Electronic and magnetic properties of Mn{sub 12} single-molecule magnets on the Au(111) surface

Energy Technology Data Exchange (ETDEWEB)

Voss, Soenke; Burgert, Michael; Fonin, Mikhail; Groth, Ulrich; Ruediger, Ulrich [Universitaet Konstanz (Germany); Michaelis, Christian; Brihuega, Ivan; Kern, Klaus [Max-Planck-Institut fuer Festkoerperforschung, Stuttgart (Germany); Dedkov, Yury S. [Institut fuer Festkoerperphysik, Technische Universitaet Dresden (Germany)

2008-07-01

The paramount interest in single-molecule magnets (SMMs) like Mn{sub 12}-acetate and its derivatives was inspired by numerous experimental and theoretical insights indicating the feasibility of addressing quantum effects of magnetism on a molecular scale. Due to its relatively high blocking temperature ({proportional_to}3 K) combined with the ability to identify well-defined spin states, Mn{sub 12} still remains the most favoured SMM possibly allowing the detection of magnetic fingerprints in transport properties of a single molecule. In this work, the electronic properties of Mn{sub 12} molecules chemically grafted on Au(111) surfaces have been studied by means of low temperature as well as room temperature scanning tunneling microscopy and spectroscopy (STS), X-ray absorption spectroscopy and photoelectron spectroscopy. The results revealed signatures from most probably intact Mn{sub 12} molecules while STS measurements in magnetic fields indicate the possibility to identify magnetic fingerprints in scanning tunneling spectra. The results will be discussed with respect to previous attempts to perform transport measurements on Mn{sub 12} SMMs.

Infrared spectroscopy of molecular submonolayers on surfaces by infrared scanning tunneling microscopy: tetramantane on Au111.

Science.gov (United States)

Pechenezhskiy, Ivan V; Hong, Xiaoping; Nguyen, Giang D; Dahl, Jeremy E P; Carlson, Robert M K; Wang, Feng; Crommie, Michael F

2013-09-20

We have developed a new scanning-tunneling-microscopy-based spectroscopy technique to characterize infrared (IR) absorption of submonolayers of molecules on conducting crystals. The technique employs a scanning tunneling microscope as a precise detector to measure the expansion of a molecule-decorated crystal that is irradiated by IR light from a tunable laser source. Using this technique, we obtain the IR absorption spectra of [121]tetramantane and [123]tetramantane on Au(111). Significant differences between the IR spectra for these two isomers show the power of this new technique to differentiate chemical structures even when single-molecule-resolved scanning tunneling microscopy (STM) images look quite similar. Furthermore, the new technique was found to yield significantly better spectral resolution than STM-based inelastic electron tunneling spectroscopy, and to allow determination of optical absorption cross sections. Compared to IR spectroscopy of bulk tetramantane powders, infrared scanning tunneling microscopy (IRSTM) spectra reveal narrower and blueshifted vibrational peaks for an ordered tetramantane adlayer. Differences between bulk and surface tetramantane vibrational spectra are explained via molecule-molecule interactions.

Single-step fabrication of electrodes with controlled nanostructured surface roughness using optically-induced electrodeposition

Science.gov (United States)

Liu, N.; Li, M.; Liu, L.; Yang, Y.; Mai, J.; Pu, H.; Sun, Y.; Li, W. J.

2018-02-01

The customized fabrication of microelectrodes from gold nanoparticles (AuNPs) has attracted much attention due to their numerous applications in chemistry and biomedical engineering, such as for surface-enhanced Raman spectroscopy (SERS) and as catalyst sites for electrochemistry. Herein, we present a novel optically-induced electrodeposition (OED) method for rapidly fabricating gold electrodes which are also surface-modified with nanoparticles in one single step. The electrodeposition mechanism, with respect to the applied AC voltage signal and the elapsed deposition time, on the resulting morphology and particle sizes was investigated. The results from SEM and AFM analysis demonstrated that 80-200 nm gold particles can be formed on the surface of the gold electrodes. Simultaneously, both the size of the nanoparticles and the roughness of the fabricated electrodes can be regulated by the deposition time. Compared to state-of-the-art methods for fabricating microelectrodes with AuNPs, such as nano-seed-mediated growth and conventional electrodeposition, this OED technique has several advantages including: (1) electrode fabrication and surface modification using nanoparticles are completed in a single step, eliminating the need for prefabricating micro electrodes; (2) the patterning of electrodes is defined using a digitally-customized, projected optical image rather than using fixed physical masks; and (3) both the fabrication and surface modification processes are rapid, and the entire fabrication process only requires less than 6 s.

Electrochemical Glucose Oxidation Using Glassy Carbon Electrodes Modified with Au-Ag Nanoparticles: Influence of Ag Content

Directory of Open Access Journals (Sweden)

Nancy Gabriela García-Morales

2015-01-01

Full Text Available This paper describes the application of glassy carbon modified electrodes bearing Aux-Agy nanoparticles to catalyze the electrochemical oxidation of glucose. In particular, the paper shows the influence of the Ag content on this oxidation process. A simple method was applied to prepare the nanoparticles, which were characterized by transmission electron microscopy, Ultraviolet-Visible spectroscopy, X-ray diffraction spectroscopy, and cyclic voltammetry. These nanoparticles were used to modify glassy carbon electrodes. The effectiveness of these electrodes for electrochemical glucose oxidation was evaluated. The modified glassy carbon electrodes are highly sensitive to glucose oxidation in alkaline media, which could be attributed to the presence of Aux-Agy nanoparticles on the electrode surface. The voltammetric results suggest that the glucose oxidation speed is controlled by the glucose diffusion to the electrode surface. These results also show that the catalytic activity of the electrodes depends on the Ag content of the nanoparticles. Best results were obtained for the Au80-Ag20 nanoparticles modified electrode. This electrode could be used for Gluconic acid (GA production.

Surface studies of Li-ion and Mg battery electrodes

Science.gov (United States)

Esbenshade, Jennifer

This dissertation focuses on studies of the surfaces of both Li-ion and Mg-ion battery electrodes. A fundamental understanding of processes occurring at the electrode surface is vital to the development of advanced battery systems. Additionally, modifications to the electrode surfaces are made and further characterized for improved performance. LiMn2O4 Cathodes for Li-ion Batteries: Effect of Mn in electrolyte on anode and Au coating to minimize dissolution: LiMn2O4 (LMO) is known to dissolve Mn ions with cycling. This section focuses on both the effect of the dissolution of Mn2+ into the electrolyte as well as Au coating on the LMO to improve electrochemical performance. Electrochemical quartz crystal microbalance (EQCM) was used to monitor changes in mass on the anode, SEM and AES were used to observe changes in surface morphology and chemical composition, and potentiostatic voltammetry was used to monitor charge and discharge capacity. The effect of Cu2+ addition in place of Mn2+ was also studied, as Cu is known to form an underpotential deposition (UPD) monolayer on Au electrodes. Following this, LMO particles were coated with a Au shell by a simple and scalable electroless deposition for use as Li-ion battery cathodes. The Au shell was intended to limit the capacity fade commonly seen with LMO cathodes by reducing the dissolution of Mn. Characterization by SEM, TEM, EELS, and AFM showed that the Au shell was approximately 3 nm thick. The Au shell prevented much of the Mn from dissolving in the electrolyte with 82% and 88% less dissolved Mn in the electrolyte at room temperature and 65 ºC, respectively, as compared to the uncoated LMO. Electrochemical performance studies with half cells showed that the Au shell maintained a higher discharge capacity over 400 cycles by nearly 30% with 110 mA hr g-1 for the 400th cycle as compared to a commercial LMO at 85 mA hr g-1. Similarly, the capacity fade was reduced in full cells: the coated LMO had 47% greater capacity

Structural design of flexible Au electrode to enable shape memory polymer for electrical actuation

Science.gov (United States)

Lu, Haibao; Lei, Ming; Zhao, Chao; Xu, Ben; Leng, Jinsong; Fu, Y. Q.

2015-04-01

An effective resistive Joule heating approach was conducted to improve the electrical actuation and shape-recovery performance of a shape memory polymer (SMP) nanocomposite. Two types of gold (Au) film patterns were deposited to be used as electrodes to drive thermal-responsive SMPs and achieve a uniform temperature distribution during electro-activated shape recovery. Furthermore, the sensing capability of the Au electrode to both mechanical and thermal stimuli applied to the SMP nanocomposite was experimentally investigated and theoretically analyzed. It was found that the change in the electrical resistance of the Au electrode could be used as an indication of shape-recovery performance. The linear response of the electrical resistance to strain was identified mainly due to the opening/closing of microcracks and their propagations in the Au electrodes during out-of-plane deformations. With an increment of thermomechanical bending cycles, the electrical resistance was increased exponentially, but it returned back to the original reading when the SMP nanocomposite returned back to its permanent shape. Finally, the flexible Au electrode enabled the actuation of the SMP nanocomposite under an electric voltage of 13.4 V, with an improved shape-recovery performance and temperature distribution.

Maleimide-activated aryl diazonium salts for electrode surface functionalization with biological and redox-active molecules.

Science.gov (United States)

Harper, Jason C; Polsky, Ronen; Wheeler, David R; Brozik, Susan M

2008-03-04

A versatile and simple method is introduced for formation of maleimide-functionalized surfaces using maleimide-activated aryl diazonium salts. We show for the first time electrodeposition of N-(4-diazophenyl)maleimide tetrafluoroborate on gold and carbon electrodes which was characterized via voltammetry, grazing angle FTIR, and ellipsometry. Electrodeposition conditions were used to control film thickness and yielded submonolayer-to-multilayer grafting. The resulting phenylmaleimide surfaces served as effective coupling agents for electrode functionalization with ferrocene and the redox-active protein cytochrome c. The utility of phenylmaleimide diazonium toward formation of a diazonium-activated conjugate, followed by direct electrodeposition of the diazonium-modified DNA onto the electrode surface, was also demonstrated. Effective electron transfer was obtained between immobilized molecules and the electrodes. This novel application of N-phenylmaleimide diazonium may facilitate the development of bioelectronic devices including biofuel cells, biosensors, and DNA and protein microarrays.

Capacitance, charge dynamics, and electrolyte-surface interactions in functionalized carbide-derived carbon electrodes

Directory of Open Access Journals (Sweden)

Boris Dyatkin

2015-12-01

Full Text Available This study analyzed the dynamics of ionic liquid electrolyte inside of defunctionalized, hydrogenated, and aminated pores of carbide-derived carbon supercapacitor electrodes. The approach tailors surface functionalities and tunes nanoporous structures to decouple the influence of pore wall composition on capacitance, ionic resistance, and long-term cyclability. Quasi-elastic neutron scattering probes the self-diffusion properties and electrode-ion interactions of electrolyte molecules confined in functionalized pores. Room-temperature ionic liquid interactions in confined pores are strongest when the hydrogen-containing groups are present on the surface. This property translates into higher capacitance and greater ion transport through pores during electrochemical cycling. Unlike hydrogenated pores, aminated pores do not favorably interact with ionic liquid ions and, subsequently, are outperformed by defunctionalized surfaces.

Capacitance, charge dynamics, and electrolyte-surface interactions in functionalized carbide-derived carbon electrodes

Energy Technology Data Exchange (ETDEWEB)

Dyatkin, Boris; Mamontov, Eugene; Cook, Kevin M.; Gogotsi, Yury

2015-12-01

This study analyzed the dynamics of ionic liquid electrolyte inside of defunctionalized, hydrogenated, and aminated pores of carbide-derived carbon supercapacitor electrodes. The approach tailors surface functionalities and tunes nanoporous structures to decouple the influence of pore wall composition on capacitance, ionic resistance, and long-term cyclability. Quasi-elastic neutron scattering probes the self-diffusion properties and electrode-ion interactions of electrolyte molecules confined in functionalized pores. Room-temperature ionic liquid interactions in confined pores are strongest when the hydrogen-containing groups are present on the surface. This property translates into higher capacitance and greater ion transport through pores during electrochemical cycling. Unlike hydrogenated pores, aminated pores do not favorably interact with ionic liquid ions and, subsequently, are outperformed by defunctionalized surfaces.

Adsorption properties of AlN on Si(111) surface: A density functional study

Science.gov (United States)

Yuan, Yinmei; Zuo, Ran; Mao, Keke; Tang, Binlong; Zhang, Zhou; Liu, Jun; Zhong, Tingting

2018-04-01

In the process of preparing GaN on Si substrate by MOCVD, an AlN buffer layer is very important. In this study, we conducted density functional theory calculations on the adsorption of AlN molecule on Si(111)-(2 × 2) surface, with the AlN molecule located horizontally or vertically above Si(111) surface at different adsorption sites. The calculations revealed that the lowest adsorption energy was at the N-top-Al-bridge site in the horizontal configuration, with the narrowest band gap, indicating that it was the most preferential adsorption growth status of AlN. In the vertical configurations, N adatom was more reactive and convenient to form bonds with the topmost Si atoms than Al adatom. When the N-end of the AlN molecule was located downward, the hollow site was the preferred adsorption site; when the Al-end was located downward, the bridge site was the most energetically favorable. Moreover, we investigated some electronic properties such as partial density of states, electron density difference, Mulliken populations, etc., revealing the microscale mechanism for AlN adsorption on Si(111) surface and providing theoretical support for adjusting the processing parameters during AlN or GaN production.

Self-assembled GaN nano-column grown on Si(111) substrate using Au+Ga alloy seeding method by metalorganic chemical vapor deposition

International Nuclear Information System (INIS)

Shim, Byung-Young; Ko, Eun-A; Song, Jae-Chul; Kang, Dong-Hun; Kim, Dong-Wook; Lee, In-Hwan; Kannappan, Santhakumar; Lee, Cheul-Ro

2007-01-01

Single-crystal GaN nano-column arrays were grown on Au-coated silicon (111) substrate by Au-Ga alloy seeding method using metalorganic chemical vapor deposition (MOCVD). The nano-column arrays were studied as a function of growth parameters and Au thin film thickness. The diameter and length of the as-grown nano-column vary from 100 to 500 nm and 4 to 6 μm, respectively. The surface morphology and optical properties of the nano-columns were investigated using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), cathodoluminescence (CL) and photoluminescence (PL). The Au+Ga alloy droplets were found to be uniformly distributed on silicon surface. Further, SEM image reveals a vertical growth and cylindrical in shape GaN nano-column. The chemical composition of the nano-column, which composed of gallium and nitrogen ions, was estimated by EDX. CL reveals a strong band edge emission from the GaN nano-column. PL spectra show a peak at 365.7 nm with a full-width half maximum (FWHM) of 65 meV which indicates good optical quality GaN nano-column with low dislocation density. Our results suggest that single crystal GaN nano-column can be grown on Au+Ga alloy on silicon substrate with a low dislocation density for better device performances. (author)

(110)-Textured Ca-doped BiFeO_3 film on refined Pt(111) electrode layer on glass substrate at reduced temperature

International Nuclear Information System (INIS)

Chang, H.W.; Shen, C.Y.; Yuan, F.T.; Tien, S.H.; Lin, S.Y.; Chen, W.A.; Wang, C.R.; Tu, C.S.; Jen, S.U.

2016-01-01

Multiferroic and photovoltaic properties of polycrystalline Bi_0_._8_5Ca_0_._1_5FeO_3 (BCFO) film on refined Pt(111) electrode buffered glass substrate have been studied. Optimized Pt(111) electrode layer having large grain size and smooth morphology enables the development of highly (110)-textured BCFO film at a temperature as low as 450 °C. The prepared BCFO film has dense microstructure, fine grain size, and smooth surface morphology. Good ferroelectric properties with the remanent polarization (2P_r) of 108 μC/cm"2 and electrical coercive field of 405 kV/cm are achieved. Improved ferromagnetic properties with magnetization of 9.2 emu/cm"3 and coercivity of 1250 Oe are also attained. Significant PV properties with open-circuit photovoltage of 0.49 V and the short-circuit photocurrent of 67.4 μA/cm"2 at illumination intensity of 228 mW/cm"2 are observed, which are comparable to BCFO ceramics or BFO epitaxial films. - Highlights: • BCFO polycrystalline film with (110) texture is formed on Pt(111) electrode. • Pt(111) underlayer induces BCFO(110) film with fine grain and flat surface. • Good multiferroic and photovoltaic properties are achieved simultaneously. • Improved multiferroic and photovoltaic properties makes BCFO film a multifunctional material for advanced applications.

Occupied and unoccupied electronic states on vicinal Si(111) surfaces decorated with monoatomic gold chains; Besetzte und unbesetzte elektronische Zustaende vizinaler Si(111)-Oberflaechen mit atomaren Goldketten

Energy Technology Data Exchange (ETDEWEB)

Biedermann, Kerstin

2012-07-12

In this work, the occupied and unoccupied electronic states of vicinal Si(111)-Au surfaces were investigated. The research focused on amending the experimental electronic band structure by two-photon photoemission and laser-based photoemission and bringing it in line with theoretical band structure calculations. This work dealt with the Si(553)-Au, the Si(111)-(5x2)-Au and the Si(557)-Au surface. Angle-resolved UV-photoelectron spectroscopy gave access to the occupied part of the band structure and thus to the energetic position, the dispersion and the symmetry of the occupied states. Bichromatic two-photon photoemission, however, revealed information about the energetics and, in addition, about the dynamics of unoccupied states on a femtosecond timescale. Notably, the selective polarization of the laser pulses allowed for distinguishing and classifying many of the states with respect to their symmetry. All three surfaces exhibited both surface and bulk states in the occupied part of the band structure. They could be clearly identified and separated from surface contributions by means of tight-binding calculations of the bulk band structure of silicon and by comparison to each other. An added similarity of these surfaces are the one-dimensional Rashba-split gold states, which definitely show dispersion along the chains but not perpendicular to them. All surfaces exhibit states which can easily be assigned to the gold chains. Additional features, however, cannot be attributed clearly to the characteristics of the complex surface reconstruction in all cases. An assignment to surface states was only successfully accomplished for Si(553)-Au. The primary emphasis of this photoemission study was on the Si(553)-Au surface, which shows the smallest defect density in comparison to the other surfaces and hence exhibits the sharpest peaks in the experimental spectra. In accordance with ab-initio band structure calculations this surface also displays, in addition to one

Reaction of the (111) faces of single-crystal indium phosphide with alkylating agents: evidence for selective reaction of the p-rich face

Energy Technology Data Exchange (ETDEWEB)

Spool, A.M.; Daube, K.A.; Mallouk, T.E.; Belmont, J.A.; Wrighton, M.S.

1986-05-28

We wish to report that the P-rich, (111)B, face of single-crystal InP, but not the In-rich, (111)A, face of the same crystal, reacts with molecular reagents to yield surface-bound material derived from the apparent alkylation of a surface P atom. Exploitation of surface functional groups has been demonstrated to be very important in the attachment of molecular reagents and polymers to electrode surfaces. Electrodes derivatized with molecules have potential uses in analysis, fuel cells, electrosynthetic cells, and photoelectrochemical cells. We now wish to present evidence showing that an important photoelectrode material, InP, can be functionalized with molecules by reaction of the P-rich, (111)B, face with alkylating reagents.

Controlled Vectorial Electron Transfer and Photoelectrochemical Applications of Layered Relay/Photosensitizer-Imprinted Au Nanoparticle Architectures on Electrodes.

Science.gov (United States)

Metzger, Tzuriel S; Tel-Vered, Ran; Willner, Itamar

2016-03-23

Two configurations of molecularly imprinted bis-aniline-bridged Au nanoparticles (NPs) for the specific binding of the electron acceptor N,N'-dimethyl-4,4'-bipyridinium (MV(2+) ) and for the photosensitizer Zn(II)-protoporphyrin IX (Zn(II)-PP-IX) are assembled on electrodes, and the photoelectrochemical features of the two configurations are discussed. Configuration I includes the MV(2+) -imprinted Au NPs matrix as a base layer, on which the Zn(II)-PP-IX-imprinted Au NPs layer is deposited, while configuration II consists of a bilayer corresponding to the reversed imprinting order. Irradiation of the two electrodes in the presence of a benzoquinone/benzohydroquinone redox probe yields photocurrents of unique features: (i) Whereas configuration I yields an anodic photocurrent, the photocurrent generated by configuration II is cathodic. (ii) The photocurrents obtained upon irradiation of the imprinted electrodes are substantially higher as compared to the nonimprinted surfaces. The high photocurrents generated by the imprinted Au NPs-modified electrodes are attributed to the effective loading of the imprinted matrices with the MV(2+) and Zn(II)-PP-IX units and to the effective charge separation proceeding in the systems. The directional anodic/cathodic photocurrents are rationalized in terms of vectorial electron transfer processes dictated by the imprinting order and by the redox potentials of the photosensitizer/electron acceptor units associated with the imprinted sites in the two configurations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Antibacterial Au nanostructured surfaces.

Science.gov (United States)

Wu, Songmei; Zuber, Flavia; Brugger, Juergen; Maniura-Weber, Katharina; Ren, Qun

2016-02-07

We present here a technological platform for engineering Au nanotopographies by templated electrodeposition on antibacterial surfaces. Three different types of nanostructures were fabricated: nanopillars, nanorings and nanonuggets. The nanopillars are the basic structures and are 50 nm in diameter and 100 nm in height. Particular arrangement of the nanopillars in various geometries formed nanorings and nanonuggets. Flat surfaces, rough substrate surfaces, and various nanostructured surfaces were compared for their abilities to attach and kill bacterial cells. Methicillin-resistant Staphylococcus aureus, a Gram-positive bacterial strain responsible for many infections in health care system, was used as the model bacterial strain. It was found that all the Au nanostructures, regardless their shapes, exhibited similar excellent antibacterial properties. A comparison of live cells attached to nanotopographic surfaces showed that the number of live S. aureus cells was flat and rough reference surfaces. Our micro/nanofabrication process is a scalable approach based on cost-efficient self-organization and provides potential for further developing functional surfaces to study the behavior of microbes on nanoscale topographies.

Dithiocarbamate Self-Assembled Monolayers as Efficient Surface Modifiers for Low Work Function Noble Metals

Energy Technology Data Exchange (ETDEWEB)

Meyer, Dominik; Schäfer, Tobias; Schulz, Philip; Jung, Sebastian; Rittich, Julia; Mokros, Daniel; Segger, Ingolf; Maercks, Franziska; Effertz, Christian; Mazzarello, Riccardo; Wuttig, Matthias

2016-09-06

Tuning the work function of the electrode is one of the crucial steps to improve charge extraction in organic electronic devices. Here, we show that N,N-dialkyl dithiocarbamates (DTC) can be effectively employed to produce low work function noble metal electrodes. Work functions between 3.1 and 3.5 eV are observed for all metals investigated (Cu, Ag, and Au). Ultraviolet photoemission spectroscopy (UPS) reveals a maximum decrease in work function by 2.1 eV as compared to the bare metal surface. Electronic structure calculations elucidate how the complex interplay between intrinsic dipoles and dipoles induced by bond formation generates such large work function shifts. Subsequently, we quantify the improvement in contact resistance of organic thin film transistor devices with DTC coated source and drain electrodes. These findings demonstrate that DTC molecules can be employed as universal surface modifiers to produce stable electrodes for electron injection in high performance hybrid organic optoelectronics.

A highly selective and sensitive cocaine aptasensor based on covalent attachment of the aptamer-functionalized AuNPs onto nanocomposite as the support platform

Energy Technology Data Exchange (ETDEWEB)

Roushani, Mahmoud, E-mail: mahmoudroushani@yahoo.com; Shahdost-fard, Faezeh

2015-01-01

Highlights: • Functionalized thiol-terminated cocaine aptamer was functionalized with AuNPs. • MWCNTs/IL/Chit was employed for covalent attachment of Apt-capture probe onto electrode. • (K{sub 3}Fe(CN){sub 6}) was used as the redox probe and DPV as analytical technique. • The aptasensor showed high sensitivity and selectivity. • Linear range from 1 nM to 11,000 nM with LOD of 100 pM for cocaine detection was obtained. - Abstract: Based on the conformational changes of the aptamer-functionalized gold nanoparticles (AuNPs) onto MWCNTs/IL/Chit nanocomposite as the support platform, we have developed a sensitive and selective electrochemical aptasensor for the detection of cocaine. The 5′-amine-3′-AuNP terminated aptamer is covalently attached to a MWCNTs/IL/Chit nanocomposite. The interaction of cocaine with the aptamer functionalized AuNP caused the aptamer to be folded and the AuNPs with negative charge at the end of the aptamer came to the near of electrode surface therefore, the electron transfer between ferricyanide (K{sub 3}Fe(CN){sub 6}) as redox probe and electrode surface was inhibited. A decreased current of (K{sub 3}Fe(CN){sub 6}) was monitored by differential pulse voltammetry technique. In an optimized condition the calibration curve for cocaine concentration was linear up to 11 μM with detection limit (signal-to-noise ratio of 3) of 100 pM. To test the selectivity of the prepared aptasensor sensing platform applicability, some analgesic drugs as the interferes were examined. The potential of the aptasensor was successfully applied for measuring cocaine concentration in human blood serum. Based on our experiments it can be said that the present method is absolutely beneficial in developing other electrochemical aptasensor.

A highly selective and sensitive cocaine aptasensor based on covalent attachment of the aptamer-functionalized AuNPs onto nanocomposite as the support platform

International Nuclear Information System (INIS)

Roushani, Mahmoud; Shahdost-fard, Faezeh

2015-01-01

Highlights: • Functionalized thiol-terminated cocaine aptamer was functionalized with AuNPs. • MWCNTs/IL/Chit was employed for covalent attachment of Apt-capture probe onto electrode. • (K 3 Fe(CN) 6 ) was used as the redox probe and DPV as analytical technique. • The aptasensor showed high sensitivity and selectivity. • Linear range from 1 nM to 11,000 nM with LOD of 100 pM for cocaine detection was obtained. - Abstract: Based on the conformational changes of the aptamer-functionalized gold nanoparticles (AuNPs) onto MWCNTs/IL/Chit nanocomposite as the support platform, we have developed a sensitive and selective electrochemical aptasensor for the detection of cocaine. The 5′-amine-3′-AuNP terminated aptamer is covalently attached to a MWCNTs/IL/Chit nanocomposite. The interaction of cocaine with the aptamer functionalized AuNP caused the aptamer to be folded and the AuNPs with negative charge at the end of the aptamer came to the near of electrode surface therefore, the electron transfer between ferricyanide (K 3 Fe(CN) 6 ) as redox probe and electrode surface was inhibited. A decreased current of (K 3 Fe(CN) 6 ) was monitored by differential pulse voltammetry technique. In an optimized condition the calibration curve for cocaine concentration was linear up to 11 μM with detection limit (signal-to-noise ratio of 3) of 100 pM. To test the selectivity of the prepared aptasensor sensing platform applicability, some analgesic drugs as the interferes were examined. The potential of the aptasensor was successfully applied for measuring cocaine concentration in human blood serum. Based on our experiments it can be said that the present method is absolutely beneficial in developing other electrochemical aptasensor

Modified Au nanoparticles-imprinted sol-gel, multiwall carbon nanotubes pencil graphite electrode used as a sensor for ranitidine determination.

Science.gov (United States)

Rezaei, B; Lotfi-Forushani, H; Ensafi, A A

2014-04-01

A new, simple, and disposable molecularly imprinted electrochemical sensor for the determination of ranitidine was developed on pencil graphite electrode (PGE) via cyclic voltammetry (CV). The PGEs were coated with MWCNTs containing the carboxylic functional group (f-MWCNTs), imprinted with sol-gel and Au nanoparticle (AuNPs) layers (AuNP/MIP-sol-gel/f-MWCNT/PGE), respectively, to enhance the electrode's electrical transmission and sensitivity. The thin film of molecularly imprinted sol-gel polymers with specific binding sites for ranitidine was cast on modified PGE by electrochemical deposition. The AuNP/MIP-sol-gel/f-MWCNT/PGE thus developed was characterized by electrochemical impedance spectroscopy (EIS) and CV. The interaction between the imprinted sensor and the target molecule was also observed on the electrode by measuring the current response of 5.0mMK3[Fe(CN)6] solution as an electrochemical probe. The pick currents of ranitidine increased linearly with concentration in the ranges of 0.05 to 2.0μM, with a detection limit of (S/N=3) 0.02μM. Finally, the modified electrode was successfully employed to determine ranitidine in human urine samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Nanoscale Polysulfides Reactors Achieved by Chemical Au-S Interaction: Improving the Performance of Li-S Batteries on the Electrode Level.

Science.gov (United States)

Fan, Chao-Ying; Xiao, Pin; Li, Huan-Huan; Wang, Hai-Feng; Zhang, Lin-Lin; Sun, Hai-Zhu; Wu, Xing-Long; Xie, Hai-Ming; Zhang, Jing-Ping

2015-12-23

In this work, the chemical interaction of cathode and lithium polysulfides (LiPSs), which is a more targeted approach for completely preventing the shuttle of LiPSs in lithium-sulfur (Li-S) batteries, has been established on the electrode level. Through simply posttreating the ordinary sulfur cathode in atmospheric environment just for several minutes, the Au nanoparticles (Au NPs) were well-decorated on/in the surface and pores of the electrode composed of commercial acetylene black (CB) and sulfur powder. The Au NPs can covalently stabilize the sulfur/LiPSs, which is advantageous for restricting the shuttle effect. Moreover, the LiPSs reservoirs of Au NPs with high conductivity can significantly control the deposition of the trapped LiPSs, contributing to the uniform distribution of sulfur species upon charging/discharging. The slight modification of the cathode with batteries. Moreover, this cathode exhibited an excellent anti-self-discharge ability. The slight decoration for the ordinary electrode, which can be easily accessed in the industrial process, provides a facile strategy for improving the performance of commercial carbon-based Li-S batteries toward practical application.

Infrared spectroscopic and voltammetric study of adsorbed CO on stepped surfaces of copper monocrystalline electrodes

International Nuclear Information System (INIS)

Koga, O.; Teruya, S.; Matsuda, K.; Minami, M.; Hoshi, N.; Hori, Y.

2005-01-01

Voltammetric and infrared (IR) spectroscopic measurements were carried out to study adsorbed CO on two series of copper single crystal electrodes n(111)-(111) and n(111)-(100) in 0.1M KH 2 PO 4 +0.1M K 2 HPO 4 at 0 o C. Reversible voltammetric waves were observed below -0.55V versus SHE for adsorption of CO which displaces preadsorbed phosphate anions. The electric charge of the redox waves is proportional to the step atom density for both single crystal series. This fact indicates that phosphate anions are specifically adsorbed on the step sites below -0.55V versus SHE. Voltammetric measurements indicated that (111) terrace of Cu is covered with adsorbed CO below -0.5V versus SHE. Nevertheless, no IR absorption band of adsorbed CO is detected from (111) terrace. Presence of adsorbed CO on (111) terrace is presumed which is not visible by the potential difference spectroscopy used in the present work. IR spectroscopic measurements showed that CO is reversibly adsorbed with an on-top manner on copper single crystal electrodes of n(111)-(111) and n(111)-(100) with approximately same wavenumber of C?O stretching vibration of 2070cm -1 . The IR band intensity is proportional to the step atom density. Thus CO is adsorbed on (111) or (100) steps on the single crystal surfaces. An analysis of the IR band intensity suggested that one CO molecule is adsorbed on every two or more Cu step atom of the monocrystalline surface. The spectroscopic data were compared with those reported for uhv system. The C-O stretching wavenumber of adsorbed CO in the electrode-electrolyte system is 30-40cm -1 lower than those in uhv system

Ternary Au/ZnO/rGO nanocomposites electrodes for high performance electrochemical storage devices

Science.gov (United States)

Chaudhary, Manchal; Doong, Ruey-an; Kumar, Nagesh; Tseng, Tseung Yuen

2017-10-01

The combination of metal and metal oxide nanoparticles with reduced graphene oxides (rGO) is an active electrode material for electrochemical storage devices. Herein, we have, for the first time, reported the fabrication of ternary Au/ZnO/rGO nanocomposites by using a rapid and environmentally friendly microwave-assisted hydrothermal method for high performance supercapacitor applications. The ZnO/rGO provides excellent electrical conductivity and good macro/mesopore structures, which can facilitate the rapid electrons and ions transport. The Au nanoparticles with particle sizes of 7-12 nm are homogeneously distributed onto the ZnO/rGO surface to enhance the electrochemical performance by retaining the capacitance at high current density. The Au/ZnO/rGO nanocomposites, prepared with the optimized rGO amount of 100 mg exhibit a high specific capacitance of 875 and 424 F g-1 at current densities of 1 and 20 A g-1, respectively, in 2 M KOH. In addition, the energy and power densities of ternary Au/ZnO/rGO can be up to 17.6-36.5 Wh kg-1 and 0.27-5.42 kW kg-1, respectively. Results obtained in this study clearly demonstrate the excellence of ternary Au/ZnO/rGO nanocomposites as the active electrode materials for electrochemical pseudocapacitor performance and can open an avenue to fabricate metal/metal oxide/rGO nanocomposites for electrochemical storage devices with both high energy and power densities.

Density functional study of a typical thiol tethered on a gold surface: ruptures under normal or parallel stretch

International Nuclear Information System (INIS)

Wang, Guan M; Sandberg, William C; Kenny, Steven D

2006-01-01

The mechanical and dynamical properties of a model Au(111)/thiol surface system were investigated by using localized atomic-type orbital density functional theory in the local density approximation. Relaxing the system gives a configuration where the sulfur atom forms covalent bonds to two adjacent gold atoms as the lowest energy structure. Investigations based on ab initio molecular dynamics simulations at 300, 350 and 370 K show that this tethering system is stable. The rupture behaviour between the thiol and the surface was studied by displacing the free end of the thiol. Calculated energy profiles show a process of multiple successive ruptures that account for experimental observations. The process features successive ruptures of the two Au-S bonds followed by the extraction of one S-bonded Au atom from the surface. The force required to rupture the thiol from the surface was found to be dependent on the direction in which the thiol was displaced, with values comparable with AFM measurements. These results aid the understanding of failure dynamics of Au(111)-thiol-tethered biosurfaces in microfluidic devices where fluidic shear and normal forces are of concern

Determination of functionalized gold nanoparticles incorporated in hydrophilic and hydrophobic microenvironments by surface modification of quartz crystal microbalance

Energy Technology Data Exchange (ETDEWEB)

Wu, Tsui-Hsun [Institute of Biomedical Engineering, College of Engineering, College of Medicine, National Taiwan University, Taipei, Taiwan, ROC (China); Institute of Medical Mechatronics, Chang Gung University, Tao-Yuan, Taiwan, ROC (China); Liao, Shu-Chuan [Center of Thin Film Technologies and Applications, Mingchi University of Technology, Taipei, Taiwan, ROC (China); Chen, Ying-Fang [Department of Dentistry, Yun-Lin Branch, National Taiwan University Hospital, Dou-Liu, Yun-Lin, Taiwan, ROC (China); Huang, Yi-You [Institute of Biomedical Engineering, College of Engineering, College of Medicine, National Taiwan University, Taipei, Taiwan, ROC (China); Wei, Yi-Syuan [Department of Materials Engineering, Tatung University, 40 Zhongshan North Road, 3rd Section, Taipei 104, Taiwan, ROC (China); Tu, Shu-Ju, E-mail: sjt@cgu.edu.tw [Department of Medical Imaging and Radiological Sciences, Chang Gung University, 259 Wen-Hwa, 1st Road, Kwei-Shan, Tao-Yuan 133, Taiwan, ROC (China); Chen, Ko-Shao, E-mail: kschen@ttu.edu.tw [Department of Materials Engineering, Tatung University, 40 Zhongshan North Road, 3rd Section, Taipei 104, Taiwan, ROC (China)

2013-06-01

In this study, plasma deposition methods were used to immobilize Au electrode of a quartz crystal microbalance (QCM) to create different microenvironments for mass measurement of various modified Au nanoparticles (AuNPs). AuNPs were modified by 11-mercaptoundecanoic acid (MUA) and 1-decanethiol (DCT) for potential applications to drug release, protective coatings, and immunosensors. We aimed to develop a highly sensitive and reliable method to quantify the mass of various modified AuNPs. The surface of AuNPs and Au electrode was coated with polymer films, as determined by Fourier transform infrared spectroscopy and atomic force microscopy. Measurements obtained for various AuNPs and the plasma-treated surface of the Au electrode were compared with those obtained for an untreated Au electrode. According to the resonant frequency shift of QCM, a linear relationship was observed that significantly differed for AuNPs, MUA-AuNPs, and DCT-AuNPs (R{sup 2} range, 0.94–0.965, 0.934–0.972, and 0.874–0.9514, respectively). Compared to inductively coupled plasma and micro-computerized tomography, the QCM method with plasma treatment has advantages of real-time monitoring, greater sensitivity, and lower cost. Our results demonstrate that surface modifications measured by a QCM system for various modified AuNPs were reliable.

Determination of functionalized gold nanoparticles incorporated in hydrophilic and hydrophobic microenvironments by surface modification of quartz crystal microbalance

International Nuclear Information System (INIS)

Wu, Tsui-Hsun; Liao, Shu-Chuan; Chen, Ying-Fang; Huang, Yi-You; Wei, Yi-Syuan; Tu, Shu-Ju; Chen, Ko-Shao

2013-01-01

In this study, plasma deposition methods were used to immobilize Au electrode of a quartz crystal microbalance (QCM) to create different microenvironments for mass measurement of various modified Au nanoparticles (AuNPs). AuNPs were modified by 11-mercaptoundecanoic acid (MUA) and 1-decanethiol (DCT) for potential applications to drug release, protective coatings, and immunosensors. We aimed to develop a highly sensitive and reliable method to quantify the mass of various modified AuNPs. The surface of AuNPs and Au electrode was coated with polymer films, as determined by Fourier transform infrared spectroscopy and atomic force microscopy. Measurements obtained for various AuNPs and the plasma-treated surface of the Au electrode were compared with those obtained for an untreated Au electrode. According to the resonant frequency shift of QCM, a linear relationship was observed that significantly differed for AuNPs, MUA-AuNPs, and DCT-AuNPs (R 2 range, 0.94–0.965, 0.934–0.972, and 0.874–0.9514, respectively). Compared to inductively coupled plasma and micro-computerized tomography, the QCM method with plasma treatment has advantages of real-time monitoring, greater sensitivity, and lower cost. Our results demonstrate that surface modifications measured by a QCM system for various modified AuNPs were reliable.

Determination of functionalized gold nanoparticles incorporated in hydrophilic and hydrophobic microenvironments by surface modification of quartz crystal microbalance

Science.gov (United States)

Wu, Tsui-Hsun; Liao, Shu-Chuan; Chen, Ying-Fang; Huang, Yi-You; Wei, Yi-Syuan; Tu, Shu-Ju; Chen, Ko-Shao

2013-06-01

In this study, plasma deposition methods were used to immobilize Au electrode of a quartz crystal microbalance (QCM) to create different microenvironments for mass measurement of various modified Au nanoparticles (AuNPs). AuNPs were modified by 11-mercaptoundecanoic acid (MUA) and 1-decanethiol (DCT) for potential applications to drug release, protective coatings, and immunosensors. We aimed to develop a highly sensitive and reliable method to quantify the mass of various modified AuNPs. The surface of AuNPs and Au electrode was coated with polymer films, as determined by Fourier transform infrared spectroscopy and atomic force microscopy. Measurements obtained for various AuNPs and the plasma-treated surface of the Au electrode were compared with those obtained for an untreated Au electrode. According to the resonant frequency shift of QCM, a linear relationship was observed that significantly differed for AuNPs, MUA-AuNPs, and DCT-AuNPs (R2 range, 0.94-0.965, 0.934-0.972, and 0.874-0.9514, respectively). Compared to inductively coupled plasma and micro-computerized tomography, the QCM method with plasma treatment has advantages of real-time monitoring, greater sensitivity, and lower cost. Our results demonstrate that surface modifications measured by a QCM system for various modified AuNPs were reliable.

Scanning tunnelling microscopy of a foldamer prototype at the liquid/solid interface : water/Au(111) versus 1-octanol/graphite

NARCIS (Netherlands)

Klymchenko, Andrey S.; Schuurmans, Norbert; van der Auweraer, Mark; Feringa, Ben L.; van Esch, Jan; De Feyter, Steven

2006-01-01

We report the design and synthesis of a catechol based foldamer containing amide functionalized alkyl chains, and its monolayer formation at the liquid/solid interface. By scanning tunnelling microscopy, both at the 1-octanol/graphite interface as well as at the water/Au( 111) interface, the

Clarification of the interaction between Au atoms and the anatase TiO2 (112) surface using density functional theory

Science.gov (United States)

Tada, Kohei; Koga, Hiroaki; Okumura, Mitsutaka; Tanaka, Shingo

2018-04-01

A model (112) surface slab of anatase TiO2 (112) was optimized, and the adsorption of Au atoms onto the (112) surface was investigated by first-principles calculations based on DFT (density functional theory) with the generalized gradient approximation (GGA). Furthermore, the results were compared with those of Au/anatase TiO2 (101) system. The (112) surface has a ridge and a groove (zig-zag structure). The Au atoms were strongly adsorbed in the grooves but became unstable as they climbed toward the ridges, and the promotion of electrons in the 5d orbitals to the 6s and 6p orbitals in the absorbed Au atom occurred. At the Au/anatase TiO2 interface, the Au-Ti4+ coordinate bond in the (112) system is stronger than that in the (101) system because the promotion of electrons is greater in the former interaction than the latter. The results suggest that Au/anatase TiO2 catalysts with a higher dispersion of Au nanoparticles could be prepared when the (112) surface is preferentially exposed.

Shape-Selective Syntheses of Gold and Copper Nanostructures: Insights From Density-Functional Theory and Molecular Dynamics

Science.gov (United States)

Liu, Shih-Hsien

Density-functional theory (DFT) and molecular dynamics (MD) were used to resolve the origins of shape-selective syntheses of {111}-faceted Au nanostructures mediated by polyvinylpyrrolidone (PVP) as well as {100}-faceted Cu nanostructures mediated by hex- adecylamine(HDA) seen in experiment. For the work in PVP on Au surfaces, the hexagonal reconstruction of Au(100) was considered. DFT results indicate that the Au(111) surface covered by the PVP segment, 2-pyrrolidone (2P), has a lower surface energy than the 2P- covered (5 x 1) Au(100)-hex surface, and that PVP may exhibit a binding affinity for Au(111) comparable to or greater than (5 x 1) Au(100)-hex. With MD, it is shown that the PVP-covered Au(111) surface has a lower surface energy than the PVP-covered (5 x 1) Au(100)-hex surface, and that the atactic PVP isosamer chains have a binding affinity for Au(111) comparable to (5 x 1) Au(100)-hex. Also, the (5 x 1) Au(100)-hex surface may have a higher flux of Au atoms than the Au(111) surface. Therefore, the Au(111) surface would be thermodynamically and kinetically favored in PVP-mediated syntheses, leading to {111}-faceted Au nanostructures. For the work in HDA on Cu surfaces, DFT results show that the HDA-covered Cu(100) surface has a slightly higher surface energy than the HDA- covered Cu(111) surface. However, HDA has a significant binding preference on Cu(100) over Cu(111). Therefore, the Cu(100) surface would be kinetically favored in HDA-mediated syn- theses, leading to {100}-faceted Cu nanostructures. Further, a metal-organic many-body (MOMB) force field for HDA-Cu interactions was developed based on the DFT work, and the force field was used to resolve the HDA binding patterns on Cu(100) at molecular level. With MD, it is found that decylamine (DA) may be used as an effective capping agent in the synthesis of {100}-faceted Cu nanostructures since DA as well as HDA are organized on Cu surfaces and have the same binding preference on Cu(100) over Cu(111

Concatenation of electrochemical grafting with chemical or electrochemical modification for preparing electrodes with specific surface functionality

International Nuclear Information System (INIS)

Verma, Pallavi; Maire, Pascal; Novak, Petr

2011-01-01

Surface modified electrodes are used in electro-analysis, electro-catalysis, sensors, biomedical applications, etc. and could also be used in batteries. The properties of modified electrodes are determined by the surface functionality. Therefore, the steps involved in the surface modification of the electrodes to obtain specific functionality are of prime importance. We illustrate here bridging of two routes of surface modifications namely electrochemical grafting, and chemical or electrochemical reduction. First, by electrochemical grafting an organic moiety is covalently immobilized on the surface. Then, either by chemical or by electrochemical route the terminal functional group of the grafted moiety is transformed. Using the former route we prepared lithium alkyl carbonate (-O(CH 2 ) 3 OCO 2 Li) modified carbon with potential applications in batteries, and employing the latter we prepared phenyl hydroxyl amine (-C 6 H 4 NHOH) modified carbon which may find application in biosensors. Benzyl alcohol (-C 6 H 4 CH 2 OH) modified carbon was prepared by both chemical as well as electrochemical route. We report combinations of conjugating the two steps of surface modifications and show how the optimal route of terminal functional group modification depends on the chemical nature of the moiety attached to the surface in the electrochemical grafting step.

Concatenation of electrochemical grafting with chemical or electrochemical modification for preparing electrodes with specific surface functionality

Energy Technology Data Exchange (ETDEWEB)

Verma, Pallavi; Maire, Pascal [Paul Scherrer Institut, Electrochemistry Laboratory, Section Electrochemical Energy Storage, CH-5232 Villigen PSI (Switzerland); Novak, Petr, E-mail: petr.novak@psi.c [Paul Scherrer Institut, Electrochemistry Laboratory, Section Electrochemical Energy Storage, CH-5232 Villigen PSI (Switzerland)

2011-04-01

Surface modified electrodes are used in electro-analysis, electro-catalysis, sensors, biomedical applications, etc. and could also be used in batteries. The properties of modified electrodes are determined by the surface functionality. Therefore, the steps involved in the surface modification of the electrodes to obtain specific functionality are of prime importance. We illustrate here bridging of two routes of surface modifications namely electrochemical grafting, and chemical or electrochemical reduction. First, by electrochemical grafting an organic moiety is covalently immobilized on the surface. Then, either by chemical or by electrochemical route the terminal functional group of the grafted moiety is transformed. Using the former route we prepared lithium alkyl carbonate (-O(CH{sub 2}){sub 3}OCO{sub 2}Li) modified carbon with potential applications in batteries, and employing the latter we prepared phenyl hydroxyl amine (-C{sub 6}H{sub 4}NHOH) modified carbon which may find application in biosensors. Benzyl alcohol (-C{sub 6}H{sub 4}CH{sub 2}OH) modified carbon was prepared by both chemical as well as electrochemical route. We report combinations of conjugating the two steps of surface modifications and show how the optimal route of terminal functional group modification depends on the chemical nature of the moiety attached to the surface in the electrochemical grafting step.

Computational investigation of CO adsorbed on Aux, Agx and (AuAg)x nanoclusters (x = 1 - 5, 147) and monometallic Au and Ag low-energy surfaces*

Science.gov (United States)

Gould, Anna L.; Catlow, C. Richard A.; Logsdail, Andrew J.

2018-02-01

Density functional theory calculations have been performed to investigate the use of CO as a probe molecule for the determination of the structure and composition of Au, Ag and AuAg nanoparticles. For very small nanoclusters (x = 1 - 5), the CO vibrational frequencies can be directly correlated to CO adsorption strength, whereas larger 147-atom nanoparticles show a strong energetic preference for CO adsorption at a vertex position but the highest wavenumbers are for the bridge positions. We also studied CO adsorption on Au and Ag (100) and (111) surfaces, for a 1 monolayer coverage, which proves to be energetically favourable on atop only and bridge positions for Au (100) and atop for Ag (100); vibrational frequencies of the CO molecules red-shift to lower wavenumbers as a result of increased metal coordination. We conclude that CO vibrational frequencies cannot be solely relied upon in order to obtain accurate compositional analysis, but we do propose that elemental rearrangement in the core@shell nanoclusters, from Ag@Au (or Au@Ag) to an alloy, would result in a shift in the CO vibrational frequencies that indicate changes in the surface composition. Contribution to the Topical Issue "Shaping Nanocatalysts", edited by Francesca Baletto, Roy L. Johnston, Jochen Blumberger and Alex Shluger.Supplementary material in the form of one pdf file available from the Journal web page at http://https://doi.org/10.1140/epjb/e2017-80280-7

Electrode quenching control for highly efficient CsPbBr3 perovskite light-emitting diodes via surface plasmon resonance and enhanced hole injection by Au nanoparticles

Science.gov (United States)

Meng, Yan; Wu, Xiaoyan; Xiong, Ziyang; Lin, Chunyan; Xiong, Zuhong; Blount, Ethan; Chen, Ping

2018-04-01

Compared to organic-inorganic hybrid metal halide perovskites, all-inorganic cesium lead halides (e.g, CsPbBr3) hold greater promise in being emissive materials for light-emitting diodes owing to their superior optoelectronic properties as well as their higher stabilities. However, there is still considerable potential for breakthroughs in the current efficiency of CsPbBr3 perovskite light-emitting diodes (PeLEDs). Electrode quenching is one of the main problems limiting the current efficiency of PeLEDs when poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) is used as the hole injection layer. In this work, electrode quenching control was realized via incorporating Au NPs into PEDOT:PSS. As a result, the CsPbBr3 PeLEDs realized an improvement in maximum luminescence ranging from ˜2348 to ˜7660 cd m-2 (˜226% enhancement) and current efficiency from 1.65 to 3.08 cd A-1 (˜86% enhancement). Such substantial enhancement of the electroluminescent performance can be attributed to effective electrode quenching control at the PEDOT:PSS/CsPbBr3 perovskite interface via the combined effects of local surface plasma resonance coupling and enhanced hole transportation in the PEDOT:PSS layer by Au nanoparticles.

Theoretical study of the surface resistivity of (111) surfaces of NixPt1-x(111) alloys

International Nuclear Information System (INIS)

Rous, P. J.

2001-01-01

A layer-Korringa - Kohn - Rostoker calculation is used to study the compositional dependence of the surface resistivity of the (111) surface of Ni x Pt 1-x (111) alloys. The compositional disorder in the bulk and at the surface is described by the coherent potential approximation. If it is assumed that the atomic planes near the (111) surface Ni x Pt 1-x have the same composition as the bulk layers, then a weak Nordheim effect is observed in the compositional dependence of the surface resistivity. However, we show that surface segregation in Ni x Pt 1-x (111) causes an inverse Nordheim dependence in the actual surface resistivity as the bulk composition is varied. [copyright] 2001 American Institute of Physics

Biofouling-resilient nanoporous gold electrodes for DNA sensing.

Science.gov (United States)

Daggumati, Pallavi; Matharu, Zimple; Wang, Ling; Seker, Erkin

2015-09-01

Electrochemical nucleic acid sensors are promising tools for point-of-care diagnostic platforms with their facile integration with electronics and scalability. However, nucleic acid detection in complex biological fluids is challenging as biomolecules nonspecifically adsorb on the electrode surface and adversely affect the sensor performance by obscuring the transport of analytes and redox species to the electrode. We report that nanoporous gold (np-Au) electrodes, prepared by a microfabrication-compatible self-assembly process and functionalized with DNA probes, enabled detection of target DNA molecules (10-200 nM) in physiologically relevant complex media (bovine serum albumin and fetal bovine serum). In contrast, the sensor performance was compromised for planar gold electrodes in the same conditions. Hybridization efficiency decreased by 10% for np-Au with coarser pores revealing a pore-size dependence of sensor performance in biofouling conditions. This nanostructure-dependent functionality in complex media suggests that the pores with the optimal size and geometry act as sieves for blocking the biomolecules from inhibiting the surfaces within the porous volume while allowing the transport of nucleic acid analytes and redox molecules.

Single-molecule conductivity of non-redox and redox molecules at pure and gold-mined Au(111)-electrode surfaces

DEFF Research Database (Denmark)

Zhang, Jingdong; Chi, Qijin; Ulstrup, Jens

The structure, two-dimensional organization, and function of molecules immobilized on solid surfaces can be addressed in a degree of detail that has reached the level of the single-molecule. In this context redox molecules are “smart” molecules adding sophisticated electronic function. Redox meta...

Intramolecular charge separation in spirobifluorene-based donor–acceptor compounds adsorbed on Au and indium tin oxide electrodes

International Nuclear Information System (INIS)

Heredia, Daniel; Otero, Luis; Gervaldo, Miguel; Fungo, Fernando; Dittrich, Thomas; Lin, Chih-Yen; Chi, Liang-Chen; Fang, Fu-Chuan; Wong, Ken-Tsung

2013-01-01

Surface photovoltage (SPV) measurements were performed with a Kelvin-probe in spirobifluorene-based donor (diphenylamine)–acceptor (dicyano or cyanoacrylic acid moieties) compounds adsorbed from highly diluted solutions onto Au and indium tin oxide electrode surfaces. Strong intramolecular charge separation (negative SPV signals up to more than 0.1 V) due to directed molecule adsorption was observed only for spirobifluorene donor–acceptor compounds with carboxylic acid moiety. SPV signals and onset energies of electronic transitions depended on ambience conditions. - Highlights: ► Fluorene donor–acceptor derivatives were adsorbed at Au and indium tin oxide. ► Surface photovoltage measurements were performed with a Kelvin-probe. ► Strong intra-molecular charge separation was observed. ► SPV signals depended on ambience conditions

Controlling noncovalent interactions between a lysine-rich α-helical peptide and self-assembled monolayers of alkanethiols on Au through functional group diversity

Energy Technology Data Exchange (ETDEWEB)

Raigoza, Annette F.; Onyirioha, Kristeen; Webb, Lauren J., E-mail: lwebb@cm.utexas.edu

2017-02-28

Highlights: • Functional variety in SAMs control covalent binding of proteins to surfaces. • Peptide density on Au(111) surfaces controlled by SAM functional groups. • Affinity between biomolecule and SAM surface follows a Langmuir isotherm. • Surface chemistry can mimic functional group diversity in proteins and peptides. - Abstract: Reliably attaching a structured biomolecule to an inorganic substrate would enable the preparation of surfaces that incorporate both biological and inorganic functions and structures. To this end, we have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to well-ordered alkanethiol self-assembled monolayers (SAM) on a Au(111) surface, in which the SAM is composed of a mixture of methyl and azide termination. Proteins, however, are composed of many diverse functional groups, and this composition directly effects protein structure, interactions, and reactivity. Here, we explore the utility of mixed SAMs with alternative terminating functional groups to tune and direct the reactivity of the surface through noncovalent peptide-surface interactions. We study both polar surfaces (OH-terminated) and charged surfaces (COOH- and NH{sub 3}-terminated, which are negatively and positively charged, respectively, under our reaction conditions). Surfaces were functionalized with a bipolar peptide composed of Lys and Leu residues that could express different interactions through either hydrophilic and/or charge (Lys) or hydrophobic (Leu) influences. X-ray photoelectron spectroscopy (XPS) and surface infrared spectroscopy were used to characterize surfaces at all stages of the peptide functionalization procedure. This strategy resulted in a high density of surface-bound α-helices without aggregation. Mixed SAMs that included a positively charged alkanethiol along with the azide-terminated thiol resulted in a more efficient reaction and better

Controlling noncovalent interactions between a lysine-rich α-helical peptide and self-assembled monolayers of alkanethiols on Au through functional group diversity

International Nuclear Information System (INIS)

Raigoza, Annette F.; Onyirioha, Kristeen; Webb, Lauren J.

2017-01-01

Highlights: • Functional variety in SAMs control covalent binding of proteins to surfaces. • Peptide density on Au(111) surfaces controlled by SAM functional groups. • Affinity between biomolecule and SAM surface follows a Langmuir isotherm. • Surface chemistry can mimic functional group diversity in proteins and peptides. - Abstract: Reliably attaching a structured biomolecule to an inorganic substrate would enable the preparation of surfaces that incorporate both biological and inorganic functions and structures. To this end, we have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to well-ordered alkanethiol self-assembled monolayers (SAM) on a Au(111) surface, in which the SAM is composed of a mixture of methyl and azide termination. Proteins, however, are composed of many diverse functional groups, and this composition directly effects protein structure, interactions, and reactivity. Here, we explore the utility of mixed SAMs with alternative terminating functional groups to tune and direct the reactivity of the surface through noncovalent peptide-surface interactions. We study both polar surfaces (OH-terminated) and charged surfaces (COOH- and NH_3-terminated, which are negatively and positively charged, respectively, under our reaction conditions). Surfaces were functionalized with a bipolar peptide composed of Lys and Leu residues that could express different interactions through either hydrophilic and/or charge (Lys) or hydrophobic (Leu) influences. X-ray photoelectron spectroscopy (XPS) and surface infrared spectroscopy were used to characterize surfaces at all stages of the peptide functionalization procedure. This strategy resulted in a high density of surface-bound α-helices without aggregation. Mixed SAMs that included a positively charged alkanethiol along with the azide-terminated thiol resulted in a more efficient reaction and better alignment

Anisotropic In Situ-Coated AuNPs on Screen-Printed Carbon Surface for Enhanced Prostate-Specific Antigen Impedimetric Aptasensor

Science.gov (United States)

Do, Tram T. N.; Van Phi, Toan; Nguy, Tin Phan; Wagner, Patrick; Eersels, Kasper; Vestergaard, Mun'delanji C.; Truong, Lien T. N.

2017-06-01

An impedimetric aptasensor has been used to study the effect of charge transfer on the binding of prostate-specific antigen (PSA) to its aptamer. Full understanding of this mechanism will be beneficial to further improve its sensitivity for PSA detection in human semen at physiologically relevant concentrations. Bare gold electrodes (SPAuEs) and gold nanoparticles (AuNPs)-coated screen-printed carbon ink electrodes (AuNPs/SPCEs) were coated with aptamer solution at various concentrations and the sensor response to increasing PSA concentration in buffer solution examined. AuNPs were deposited onto carbon electrodes in 10 cycles. AuNPs/SPCEs were then coated with a self-assembled monolayer (SAM) of 16-mercaptohexadecanoic acid prior to aptamer immobilization at dose of 5 μg mL-1. The results indicate that anisotropic AuNPs/SPCEs outperform bare gold electrodes in terms of decreased amount of aptamer bunches as well as the number of intermediate PSA-aptamer complexes formed on the electrode surface. The key finding is that the fabricated aptasensor is sensitive enough [limit of detection (LoD) 1.95 ng mL-1] for early diagnosis of prostate cancer and displays linear response in the physiologically relevant concentration range (0 ng mL-1 to 10 ng mL-1), as shown by the calibration curve of the relative change in electron transfer resistance (Δ R CT) versus PSA concentration when aptamer/SAM/AuNPs/SPCEs were exposed to buffer containing PSA at different concentrations.

Smooth-surface silver nanowire electrode with high conductivity and transparency on functional layer coated flexible film

Energy Technology Data Exchange (ETDEWEB)

Lee, So Hee; Lim, Sooman; Kim, Haekyoung, E-mail: hkkim@ynu.ac.kr

2015-08-31

Transparent conductive electrode (TCE) with silver nanowires has been widely studied as an alternative of indium tin oxide for flexible electronic or optical devices such as organic light-emitting diodes, and solar cells. However, it has an issue of surface roughness due to nanowire's intrinsic properties. Here, to achieve a smooth electrode with high conductivity and transmittance on polyethylene terephthalate (PET) substrates, a functional layer of poly(N-vinylpyrrolidone) (PVP) is utilized with a mechanical transfer process. The silver nanowire electrode on PVP-coated PET with low surface roughness of 9 nm exhibits the low sheet resistance of 18 Ω □{sup −1} and high transmittance of 87.6%. It is produced by transferring the silver nanowire electrode spin-coated on the glass to PVP-coated PET using a pressure of 10 MPa for 10 min. Silver nanowire electrode on PVP-coated PET demonstrates the stable sheet resistance of 18 Ω □{sup −1} after the mechanical taping test due to strong adhesion between PVP functional layer and silver nanowires. Smooth TCE with silver nanowires could be proposed as a transparent electrode for flexible electronic or optical devices, which consist of thin electrical active layers on TCE. - Highlights: • Silver nanowire (Ag NWs) transparent electrodes were fabricated on flexible film. • Flexible film was coated with poly N-vinylpyrrolidone (PVP). • PVP layer plays roles as an adhesive layer and matrix in electrode. • Ag NWs electrode exhibited with low surface roughness of 9 nm. • Ag NWs electrode has a low resistance (18 Ω ☐{sup −1}) and high transmittance (87.6%)

Smooth-surface silver nanowire electrode with high conductivity and transparency on functional layer coated flexible film

International Nuclear Information System (INIS)

Lee, So Hee; Lim, Sooman; Kim, Haekyoung

2015-01-01

Transparent conductive electrode (TCE) with silver nanowires has been widely studied as an alternative of indium tin oxide for flexible electronic or optical devices such as organic light-emitting diodes, and solar cells. However, it has an issue of surface roughness due to nanowire's intrinsic properties. Here, to achieve a smooth electrode with high conductivity and transmittance on polyethylene terephthalate (PET) substrates, a functional layer of poly(N-vinylpyrrolidone) (PVP) is utilized with a mechanical transfer process. The silver nanowire electrode on PVP-coated PET with low surface roughness of 9 nm exhibits the low sheet resistance of 18 Ω □ −1 and high transmittance of 87.6%. It is produced by transferring the silver nanowire electrode spin-coated on the glass to PVP-coated PET using a pressure of 10 MPa for 10 min. Silver nanowire electrode on PVP-coated PET demonstrates the stable sheet resistance of 18 Ω □ −1 after the mechanical taping test due to strong adhesion between PVP functional layer and silver nanowires. Smooth TCE with silver nanowires could be proposed as a transparent electrode for flexible electronic or optical devices, which consist of thin electrical active layers on TCE. - Highlights: • Silver nanowire (Ag NWs) transparent electrodes were fabricated on flexible film. • Flexible film was coated with poly N-vinylpyrrolidone (PVP). • PVP layer plays roles as an adhesive layer and matrix in electrode. • Ag NWs electrode exhibited with low surface roughness of 9 nm. • Ag NWs electrode has a low resistance (18 Ω ☐ −1 ) and high transmittance (87.6%)

Interaction of Au with thin ZrO2 films: influence of ZrO2 morphology on the adsorption and thermal stability of Au nanoparticles.

Science.gov (United States)

Pan, Yonghe; Gao, Yan; Kong, Dandan; Wang, Guodong; Hou, Jianbo; Hu, Shanwei; Pan, Haibin; Zhu, Junfa

2012-04-10

The model catalysts of ZrO(2)-supported Au nanoparticles have been prepared by deposition of Au atoms onto the surfaces of thin ZrO(2) films with different morphologies. The adsorption and thermal stability of Au nanoparticles on thin ZrO(2) films have been investigated using synchrotron radiation photoemission spectroscopy (SRPES) and X-ray photoelectron spectroscopy (XPS). The thin ZrO(2) films were prepared by two different methods, giving rise to different morphologies. The first method utilized wet chemical impregnation to synthesize the thin ZrO(2) film through the procedure of first spin-coating a zirconium ethoxide (Zr(OC(2)H(5))(4)) precursor onto a SiO(2)/Si(100) substrate at room temperature followed by calcination at 773 K for 12 h. Scanning electron microscopy (SEM) investigations indicate that highly porous "sponge-like nanostructures" were obtained in this case. The second method was epitaxial growth of a ZrO(2)(111) film through vacuum evaporation of Zr metal onto Pt(111) in 1 × 10(-6) Torr of oxygen at 550 K followed by annealing at 1000 K. The structural analysis with low energy electron diffraction (LEED) of this film exhibits good long-range ordering. It has been found that Au forms smaller particles on the porous ZrO(2) film as compared to those on the ordered ZrO(2)(111) film at a given coverage. Thermal annealing experiments demonstrate that Au particles are more thermally stable on the porous ZrO(2) surface than on the ZrO(2)(111) surface, although on both surfaces, Au particles experience significant sintering at elevated temperatures. In addition, by annealing the surfaces to 1100 K, Au particles desorb completely from ZrO(2)(111) but not from porous ZrO(2). The enhanced thermal stability for Au on porous ZrO(2) can be attributed to the stronger interaction of the adsorbed Au with the defects and the hindered migration or coalescence resulting from the porous structures. © 2012 American Chemical Society

Pentacene Multilayers On Ag(111) Surface

International Nuclear Information System (INIS)

Mete, E.

2010-01-01

The structural profiles and electronic properties of pentacene (C 2 2H 1 4) multilayers on Ag(111) surface has been studied within the density functional theory (DFT) framework. We have performed first-principle total energy calculations based on the projector augmented wave (PAW) method to investigate the initial growth patterns of pentacene (Pn) on Ag(111) surface. In its bulk phase, pentacene crystallizes with a triclinic symmetry while a thin film phase having an orthorhombic unit cell is energetically less favorable by 0.12 eV/cell. Pentacene prefers to stay planar on Ag(111) surface and aligns perfectly along lattice vector (1,-1,0) without any molecular deformation at a height of 3.9 angstroms. At one monolayer (ML) coverage the separation between the molecular layer and the surface plane extends to 4.1 angstroms due to intermolecular interactions weakening surface-pentacene attraction. While the first ML remains flat, the molecules on a second full pentacene layer deposited on the surface rearrange so that they become skewed with respect to each other. This adsorption mode is energetically more preferable than the one for which the molecules form a flat pentacene layer by an energy difference similar to that obtained for bulk and thin film phases. Moreover, as new layers added, pentacenes assemble to maintain this skewness for 3 and 4 ML similar to its bulk phase while the first ML always remains flat. Therefore, our calculations indicate bulk-like initial stages for the growth pattern.

The fabrication and single electron transport of Au nano-particles placed between Nb nanogap electrodes

International Nuclear Information System (INIS)

Nishino, T; Negishi, R; Ishibashi, K; Kawao, M; Nagata, T; Ozawa, H

2010-01-01

We have fabricated Nb nanogap electrodes using a combination of molecular lithography and electron beam lithography. Au nano-particles with anchor molecules were placed in the gap, the width of which could be controlled on a molecular scale (∼2 nm). Three different anchor molecules which connect the Au nano-particles and the electrodes were tested to investigate their contact resistance, and a local gate was fabricated underneath the Au nano-particles. The electrical transport measurements at liquid helium temperatures indicated single electron transistor (SET) characteristics with a charging energy of about ∼ 5 meV, and a clear indication of the effect of superconducting electrodes was not observed, possibly due to the large tunnel resistance.

A comparative study of the adsorption and oxidation of L-alanine and L-serine on Au(1 0 0), Au(1 1 1) and gold thin film electrodes in acid media

International Nuclear Information System (INIS)

Sandoval, Andrea P.; Orts, José Manuel; Rodes, Antonio; Feliu, Juan M.

2013-01-01

The adsorption and oxidation of L-alanine and L-serine at Au(1 1 1) and Au(1 0 0) single crystal and evaporated thin-film electrodes with preferential (1 1 1) orientation was studied in perchloric acid solutions. For this purpose, cyclic voltammetry experiments were combined with external reflection infrared spectroscopy (gold single crystals) and surface-enhanced infrared reflection–absorption spectroscopy under attenuated total reflection conditions (ATR-SEIRAS) (gold thin films). In addition, theoretical harmonic vibrational frequencies, obtained from B3LYP/LANL2DZ, 6-31+G(d) calculations for the zwitterionic species adsorbed on Au clusters with (1 1 1) orientation, were used to interpret the experimental spectra. The optimized geometry obtained from DFT calculations for the corresponding zwitterion plus a water molecule, under the application of an external electric field of 0.01 a.u. corresponds to a bidentate asymmetrical bridge adsorption configuration. The absence of an adsorbate band for the asymmetric OCO stretching in the experimental infrared spectra confirms the bidentate bonding of the adsorbed zwitterion through the oxygen atoms of the carboxylate group irrespective of the crystallographic orientation of the electrode surface, the adsorbate coverage and the electrode potential. In addition to typical interfacial water bands associated to perchlorate anions, which are co-adsorbed in order to compensate the positive charge of the ammonium group, the ATR-SEIRA spectra also show bands around 2950 cm −1 that can be related to the formation of hydrogen bonds between interfacial water and the ammonium group of the adsorbed zwitterion. The voltammetric experiments have shown that, as in the case of platinum electrodes, L-serine oxidizes at lower potentials than L-alanine. Under these conditions, the in situ infrared experiments show the formation of carbon dioxide and adsorbed cyanide as oxidation products of L-serine. In the case of L-alanine, only

Characterization and methanol electrooxidation studies of Pt(111)/Os surfaces prepared by spontaneous deposition.

Science.gov (United States)

Johnston, Christina M; Strbac, Svetlana; Lewera, Adam; Sibert, Eric; Wieckowski, Andrzej

2006-09-12

Catalytic activity of the Pt(111)/Os surface toward methanol electrooxidation was optimized by exploring a wide range of Os coverage. Various methods of surface analyses were used, including electroanalytical, STM, and XPS methods. The Pt(111) surface was decorated with nanosized Os islands by spontaneous deposition, and the Os coverage was controlled by changing the exposure time to the Os-containing electrolyte. The structure of Os deposits on Pt(111) was characterized and quantified by in situ STM and stripping voltammetry. We found that the optimal Os surface coverage of Pt(111) for methanol electrooxidation was 0.7 +/- 0.1 ML, close to 1.0 +/- 0.1 Os packing density. Apparently, the high osmium coverage Pt(111)/Os surface provides more of the necessary oxygen-containing species (e.g., Os-OH) for effective methanol electrooxidation than the Pt(111)/Os surfaces with lower Os coverage (vs e.g., Ru-OH). Supporting evidence for this conjecture comes from the CO electrooxidation data, which show that the onset potential for CO stripping is lowered from 0.53 to 0.45 V when the Os coverage is increased from 0.2 to 0.7 ML. However, the activity of Pt(111)/Os for methanol electrooxidation decreases when the Os coverage is higher than 0.7 +/- 0.1 ML, indicating that Pt sites uncovered by Os are necessary for sustaining significant methanol oxidation rates. Furthermore, osmium is inactive for methanol electrooxidation when the platinum substrate is absent: Os deposits on Au(111), a bulk Os ingot, and thick films of electrodeposited Os on Pt(111), all compare poorly to Pt(111)/Os. We conclude that a bifunctional mechanism applies to the methanol electrooxidation similarly to Pt(111)/Ru, although with fewer available Pt sites. Finally, the potential window for methanol electrooxidation on Pt(111)/Os was observed to shift positively versus Pt(111)/Ru. Because of the difference in the Os and Ru oxophilicity under electrochemical conditions, the Os deposit provides fewer

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

International Nuclear Information System (INIS)

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

2010-01-01

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 (E F ), 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 E F . 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.

Preparation of Au nanosheets supported on Ni foam and its electrocatalytic performance towards NaBH4 oxidation

International Nuclear Information System (INIS)

Yang, Fan; Cheng, Kui; Wang, Guiling; Cao, Dianxue

2015-01-01

Highlights: • The unique Au nanosheets are electrodeposited uniformly on Ni foam substrate. • Au NSs/Ni foam electrode shows high catalytic activity for NaBH 4 electrooxidation. • The surface of a single Au sheet is consisted of many nano-scale corrugations. - Abstract: The unique Au nanosheets (Au NSs) are electrodeposited uniformly on Ni foam substrate via a one-step potentiostatic electrodeposition technique. The electrode is characterized by scanning electron microscopy equipped with energy dispersive X-ray spectrometer and X-ray diffractometer. It shows a unique open structure allowing the full utilization of Au surface active sites. NaBH 4 electrooxidation in KOH solution on the Au NSs/Ni foam electrode are studied by linear sweep voltammetry and chronoamperometry. The electrode exhibits a high catalytic performance outperforming the Au particles made by the same method. At the oxidation potential of 0 V, the current density of 827 mA cm −2 can be achieved on Au NSs/Ni foam electrode, and only 219 mA cm −2 was obtained on Au NPs/Ni foam electrode, indicating that the catalytic activity is increased by 278%, which is attributed to the porous 3D structure, ensuring the full utilization of Au surfaces. Besides, H 2 generated by NaBH 4 hydrolysis can quickly diffuse away from the electrode, preventing surface active sites of Au from blocking by adsorbed gas bubbles

Electrochemical and AFM characterization on gold and carbon electrodes of a high redox potential laccase from Fusarium proliferatum.

Science.gov (United States)

González Arzola, K; Gimeno, Y; Arévalo, M C; Falcón, M A; Hernández Creus, A

2010-08-01

The redox potential of the T1 copper site of laccase from Fusarium proliferatum was determined by titration to be about 510 mV vs. SCE (750 mV vs. NHE), which makes it a high redox potential enzyme. Anaerobic electron transfer reactions between laccase and carbon and gold electrodes were detected, both in solution and when the enzyme was adsorbed on these surfaces. In solution, a single high-potential signal (660 mV vs. SCE) was recorded at the carbon surfaces, attributable to the T1 copper site of the enzyme. However, a well-defined oxidative process at about 660 mV and an anodic wave at 350 mV vs. SCE were recorded at the gold electrode, respectively associated with the T1 and T2 copper sites. Laccase-modified carbon electrodes behaved analogously when the enzyme was in solution, unlike laccase adsorbed on gold, which showed only a low-potential signal. Laccase molecules were successfully imaged by AFM; obtaining a thick compact stable film on Au(111), and large aggregates forming a complex network of small branches leaving voids on the HOPG surface. Laccase-modified carbon electrodes retained significant enzymatic activity, efficiently oxidising violuric acid and reducing molecular oxygen. Explanations are proposed for how protein-film organisation affects the electrode function. Copyright (c) 2009 Elsevier B.V. All rights reserved.

The effect of the adsorbate layer on the work function reduction of gold substrates under external electric fields

Science.gov (United States)

He, Xiang; Cheng, Feng; Chen, Zhao-Xu

2017-12-01

The interface interaction between the dimethyl sulfide (DMS) molecule and the gold substrate under external electric fields is investigated by density functional theory method. The polarized DMS adsorbate reduces the work function of the gold substrate while the induced substrate dipole upon the adsorption slightly increases the work function. The DMS layer partially shields the Au(111) substrate from the electric fields and the vacuum level of DMS/Au(111) shifts less than of Au(111) in consequence. Under electric fields pointing outward from the Au(111) surface, both the reduction of work function and the adsorption of DMS molecule are enhanced on the surface. We also suggest the possible application of the field-effect transistor (FET) sensor with gold gate for detecting DMS molecule by utilizing the reduction of substrate work function upon adsorption. The effects of coverage and electric field on the theoretical sensitivity of the sensor are also discussed.

The Enhanced Photo-Electrochemical Detection of Uric Acid on Au Nanoparticles Modified Glassy Carbon Electrode

Science.gov (United States)

Shi, Yuting; Wang, Jin; Li, Shumin; Yan, Bo; Xu, Hui; Zhang, Ke; Du, Yukou

2017-07-01

In this work, a sensitive and novel method for determining uric acid (UA) has been developed, in which the glassy carbon electrode (GCE) was modified with electrodeposition Au nanoparticles and used to monitor the concentration of UA with the assistant of visible light illumination. The morphology of the Au nanoparticles deposited on GCE surface were characterized by scanning electron microscope (SEM) and the nanoparticles were found to be well-dispersed spheres with the average diameter approaching 26.1 nm. A series of cyclic voltammetry (CV) and differential pulse voltammetry (DPV) measurements have revealed that the introduction of visible light can greatly enhance both the strength and stability of response current due to the surface plasmon resonance (SPR). Specifically, the DPV showed a linear relationship between peak current and UA concentration in the range of 2.8 to 57.5 μM with the equation of I pa (μA) = 0.0121 c UA (μM) + 0.3122 ( R 2 = 0.9987). Herein, the visible light illuminated Au/GCE possesses a potential to be a sensitive electrochemical sensor in the future.

Diffusion of single Au, Ag and Cu atoms inside Si(111)-(7 × 7) half unit cells: A comparative study

Energy Technology Data Exchange (ETDEWEB)

Liu, Qin [Department of Physics, Southern University of Science and Technology, Shenzhen, Guangdong 518055 (China); Department of Physics, The Chinese University of Hong Kong, Shatin, New Territory, Hong Kong (China); Science and Technology on Surface Physics and Chemistry Laboratory, Mianyang, Sichuan 621908 (China); Fu, Qiang [Institut für Physik and IRIS Adlershof, Humboldt-Universität zu Berlin, Zum Großen Windkanal 6, 12489 Berlin (Germany); Shao, Xiji; Ma, Xuhang; Wu, Xuefeng [Department of Physics, Southern University of Science and Technology, Shenzhen, Guangdong 518055 (China); Wang, Kedong, E-mail: wangkd@sustc.edu.cn [Department of Physics, Southern University of Science and Technology, Shenzhen, Guangdong 518055 (China); Xiao, Xudong, E-mail: xdxiao@phy.cuhk.edu.hk [Department of Physics, The Chinese University of Hong Kong, Shatin, New Territory, Hong Kong (China)

2017-04-15

Highlights: • Diffusions of Au, Ag and Cu atoms in the half unit cells of Si(111)-(7×7) have been studied by using a STM-based I-t method. • Despite their similar absorption sites, the diffusion dynamics show obvious differences between Ag and the other two. • Theoretical calculations suggest that different potential energy profiles are responsible for the observed differences. - Abstract: The diffusion behaviors of single Au, Ag and Cu atoms on Si(111)-(7 × 7) half unit cells have been investigated via combining scanning tunneling microscopy and first-principles calculations. Despite the similar adsorption sites between both half unit cells among these elements, the diffusion dynamics show obvious differences between Ag and the other two. Although obvious asymmetry has been found in the diffusion behaviors of Au and Cu atoms in two half unit cells of Si(111)-(7 × 7), the asymmetry behaves in a way different from that of Ag atoms and no dual-time character has been observed for the diffusions of Au and Cu in both half unit cells. Theoretical calculations suggest a different potential energy profile caused by the stronger hybridization between d states of Au (Cu) and Si states make the concept of basin useless for the diffusion of Au and Cu atoms inside the half unit cells of Si(111)-(7 × 7).

Density functional theory studies of the adsorption of ethylene and oxygen on Pt(111) and Pt3Sn(111)

DEFF Research Database (Denmark)

Watwe, R.M.; Cortright, R.D.; Mavrikakis, Manos

2001-01-01

Density functional theory, employing periodic slab calculations, was used to investigate the interactions of ethylene and oxygen with Pt(111) and Pt3Sn(111). The predicted energetics and structures of adsorbed species on Pt(111) are in good agreement with experimental data. The binding energies...... more than adsorption on two-fold and one-fold sites. Oxygen atoms bond as strongly on Pt3Sn(111) as on Pt(111), and these atoms prefer to adsorb near Sn atoms on the surface. The addition of Sn to Pt(111) leads to a surface heterogeneity, wherein ethylidyne species prefer to adsorb away from Sn atoms...

Flexible nonvolatile memory devices based on Au/PMMA nanocomposites deposited on PEDOT:PSS/Ag nanowire hybrid electrodes

International Nuclear Information System (INIS)

Sung, Sihyun; Kim, Tae Whan

2017-01-01

Highlights: • Flexible nonvolatile memory (NVM) devices fabricated utilizing Au nanoparticles (AuNPs) embedded in a PMMA layer were fabricated. • The insertion of the PEDOT:PSS layer enhanced the surface uniformity of the AgNW bottom electrode, resulting in improved device performances. • Current-voltage curves for the Al/PMMA:AuNP/PEDOT:PSS/AgNW/PET devices showed clockwise current hysteresis behaviors. • ON/OFF ratio of 1 × 10 3 was maintained for retention times longer than 1 × 10 4 s. • Memory characteristics of the NVM devices before and after bending were similar. - Abstract: Flexible nonvolatile memory (NVM) devices fabricated utilizing Au nanoparticles (AuNPs) embedded in a poly(methylmethacrylate) (PMMA) layer were fabricated on a silver nanowire (AgNW) or a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/AgNW coated on poly(ethylene terephthalate) (PET) substrates. The transmittance and the sheet resistance of the PEDOT:PSS/AgNW hybrid layer were approximately 89% and 50 Ω/sq, respectively, which were comparable to the values for commercial indium-tin-oxide (ITO) electrodes. Current-voltage curves for the Al/PMMA:AuNP/PEDOT:PSS/AgNW/PET devices at 300 K showed clockwise current hysteresis behaviors due to the existence of the AuNPs. The endurance number of ON/OFF switching for the NVM devices was above 30 cycles. An ON/OFF ratio of 1 × 10 3 was maintained for retention times longer than 1 × 10 4 s. The maximum memory margins of the NVM devices before and after bending were approximately 3.4 × 10 3 and 1.4 × 10 3 , respectively. The retention times of the devices before and after bending remained same 1 × 10 4 s. The memory margin and the stability of flexible NVMs fabricated on AgNW electrodes were enhanced due to the embedded PEDOT:PSS buffer layer.

Flexible nonvolatile memory devices based on Au/PMMA nanocomposites deposited on PEDOT:PSS/Ag nanowire hybrid electrodes

Energy Technology Data Exchange (ETDEWEB)

Sung, Sihyun; Kim, Tae Whan, E-mail: twk@hanyang.ac.kr

2017-07-31

Highlights: • Flexible nonvolatile memory (NVM) devices fabricated utilizing Au nanoparticles (AuNPs) embedded in a PMMA layer were fabricated. • The insertion of the PEDOT:PSS layer enhanced the surface uniformity of the AgNW bottom electrode, resulting in improved device performances. • Current-voltage curves for the Al/PMMA:AuNP/PEDOT:PSS/AgNW/PET devices showed clockwise current hysteresis behaviors. • ON/OFF ratio of 1 × 10{sup 3} was maintained for retention times longer than 1 × 10{sup 4} s. • Memory characteristics of the NVM devices before and after bending were similar. - Abstract: Flexible nonvolatile memory (NVM) devices fabricated utilizing Au nanoparticles (AuNPs) embedded in a poly(methylmethacrylate) (PMMA) layer were fabricated on a silver nanowire (AgNW) or a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/AgNW coated on poly(ethylene terephthalate) (PET) substrates. The transmittance and the sheet resistance of the PEDOT:PSS/AgNW hybrid layer were approximately 89% and 50 Ω/sq, respectively, which were comparable to the values for commercial indium-tin-oxide (ITO) electrodes. Current-voltage curves for the Al/PMMA:AuNP/PEDOT:PSS/AgNW/PET devices at 300 K showed clockwise current hysteresis behaviors due to the existence of the AuNPs. The endurance number of ON/OFF switching for the NVM devices was above 30 cycles. An ON/OFF ratio of 1 × 10{sup 3} was maintained for retention times longer than 1 × 10{sup 4} s. The maximum memory margins of the NVM devices before and after bending were approximately 3.4 × 10{sup 3} and 1.4 × 10{sup 3}, respectively. The retention times of the devices before and after bending remained same 1 × 10{sup 4} s. The memory margin and the stability of flexible NVMs fabricated on AgNW electrodes were enhanced due to the embedded PEDOT:PSS buffer layer.

Polymyxin-coated Au and carbon nanotube electrodes for stable [NiFe]-hydrogenase film voltammetry.

NARCIS (Netherlands)

Hoeben, F.J.M.; Heller, I.; Albracht, S.P.J.; Dekker, C.; Lemay, S.G.; Heering, H.A.

2008-01-01

We report on the use of polymyxin (PM), a cyclic cationic lipodecapeptide, as an electrode modifier for studying protein film voltammetry (PFV) on Au and single-walled carbon nanotube (SWNT) electrodes. Pretreating the electrodes with PM allows for the subsequent immobilization of an active

Hydrogen-bonded clusters of 1, 1'-ferrocenedicarboxylic acid on Au(111) are initially formed in solution

Science.gov (United States)

Quardokus, Rebecca C.; Wasio, Natalie A.; Brown, Ryan D.; Christie, John A.; Henderson, Kenneth W.; Forrest, Ryan P.; Lent, Craig S.; Corcelli, Steven A.; Alex Kandel, S.

2015-03-01

Low-temperature scanning tunneling microscopy is used to observe self-assembled structures of ferrocenedicarboxylic acid (Fc(COOH)2) on the Au(111) surface. The surface is prepared by pulse-deposition of Fc(COOH)2 dissolved in methanol, and the solvent is evaporated before imaging. While the rows of hydrogen-bonded dimers that are common for carboxylic acid species are observed, the majority of adsorbed Fc(COOH)2 is instead found in six-molecule clusters with a well-defined and chiral geometry. The coverage and distribution of these clusters are consistent with a random sequential adsorption model, showing that solution-phase species are determinative of adsorbate distribution for this system under these reaction conditions.

Gold Mining by Alkanethiol Radicals: Vacancies and Pits in the Self-Assembled Monolayers of 1-Propanethiol and 1-Butanethiol on Au(111)

DEFF Research Database (Denmark)

Wang, Yun; Chi, Qijin; Hush, Noel S.

2011-01-01

Scanning-tunneling microscopy (STM) under electrochemical control (in situ STM) in aqueous solution, combined with a priori density functional theory (DFT) image simulations at room temperature, reveals the atomic nature of the interface between Au(111) and self-assembled monolayers (SAMs) of 1-p...

Functionalization of indium-tin-oxide electrodes by laser-nanostructured gold thin films for biosensing applications

Energy Technology Data Exchange (ETDEWEB)

Grochowska, Katarzyna, E-mail: kgrochowska@imp.gda.pl [Centre for Plasma and Laser Engineering, The Szewalski Institute, Polish Academy of Sciences, 14 Fiszera St, 80-231 Gdańsk (Poland); Siuzdak, Katarzyna [Centre for Plasma and Laser Engineering, The Szewalski Institute, Polish Academy of Sciences, 14 Fiszera St, 80-231 Gdańsk (Poland); Karczewski, Jakub [Solid State Physics Department, Faculty of Applied Physics and Mathematics, Gdańsk University of Technology, 11/12 Narutowicza St, 80-233, Gdańsk (Poland); Śliwiński, Gerard [Centre for Plasma and Laser Engineering, The Szewalski Institute, Polish Academy of Sciences, 14 Fiszera St, 80-231 Gdańsk (Poland)

2015-12-01

Graphical abstract: - Highlights: • ITO electrodes modified by NP arrays prepared by laser dewetting of thin Au films. • Enhanced activity, linear response and high sensitivity towards glucose. • Promising biosensor material AuNP-modified ITO of improved performance. - Abstract: The production and properties of the indium-tin-oxide (ITO) electrodes functionalized by Au nanoparticle (NP) arrays of a relatively large area formed by pulsed laser nanostructuring of thin gold films are reported and discussed. The SEM inspection of modified electrodes reveals the presence of the nearly spherical and disc-shaped particles of dimensions in the range of 40–120 nm. The NP-array geometry can be controlled by selection of the laser processing conditions. It is shown that particle size and packing density of the array are important factors which determine the electrode performance. In the case of NP-modified electrodes the peak current corresponding to the glucose direct oxidation process shows rise with increasing glucose concentration markedly higher comparing to the reference Au disc electrode. The detection limit reaches 12 μM and linear response of the sensor is observed from 0.1 to 47 mM that covers the normal physiological range of the blood sugar detection.

Systematic Control of Self-Assembled Au Nanoparticles and Nanostructures Through the Variation of Deposition Amount, Annealing Duration, and Temperature on Si (111).

Science.gov (United States)

Li, Ming-Yu; Sui, Mao; Pandey, Puran; Zhang, Quanzhen; Kim, Eun-Soo; Lee, Jihoon

2015-12-01

The size, density, and configurations of Au nanoparticles (NPs) can play important roles in controlling the electron mobility, light absorption, and localized surface plasmon resonance, and further in the Au NP-assisted nanostructure fabrications. In this study, we present a systematical investigation on the evolution of Au NPs and nanostructures on Si (111) by controlling the deposition amount (DA), annealing temperature (AT), and dwelling time (DT). Under an identical growth condition, the morphologies of Au NPs and nanostructures drastically evolve when the DA is only slightly varied, based on the Volmer-Weber and coalescence models: i.e. I: mini NPs, II: mid-sized round dome-shaped Au NPs, III: large Au NPs, and IV: coalesced nanostructures. With the AT control, three distinctive ranges are observed: i.e., NP nucleation, Au NPs maturation and melting. The gradual dimensional expansion of Au NPs is always compensated with the density reduction, which is explained with the thermodynamic theory. The DT effect is relatively minor on Au NPs, a sharp contrast to other metallic NPs, which is discussed based on the Ostwald-ripening.

Surface photovoltage investigation of gold chains on Si(111) by two-photon photoemission

Energy Technology Data Exchange (ETDEWEB)

Otto, Sebastian; Biedermann, Kerstin; Fauster, Thomas [Lehrstuhl fuer Festkoerperphysik, Universitaet Erlangen-Nuernberg, Staudtstr. 7, D-91058 Erlangen (Germany)

2011-07-01

We present surface photovoltage measurements on Si(111)-(7 x 7) with monoatomic gold chains. The gold coverage was varied between zero and 0.6 ML, where the Si(111)-(5 x 2)-Au reconstruction covers the surface completely. During the two-photon photoemission experiments the p- or n-doped samples were illuminated by infrared (IR, E{sub IR}=1.55 eV) and ultraviolet (UV, E{sub UV}=4.65 eV) laser pulses. For all coverages the photovoltage was determined for sample temperatures of 90 K and 300 K by variation of the IR and UV laser power. P-doped as well as n-doped Si(111) wafers show a linear dependence of the photovoltage on gold coverage. This stands in contrast to scanning tunneling spectroscopy measurements, which show a coverage-independent photovoltage over a wide coverage range for n-doped wafers. While for p-doped wafers our experimentally determined photovoltage is in agreement with previous reports, for n-doped wafers the observed values are lower than expected.

In situ surface X-ray diffraction study of ultrathin epitaxial Co films on Au(111) in alkaline solution

International Nuclear Information System (INIS)

Reikowski, Finn; Maroun, Fouad; Di, Nan; Allongue, Philippe; Ruge, Martin; Stettner, Jochim; Magnussen, Olaf M.

2016-01-01

The oxidation behavior of ultrathin electrodeposited Co films on Au(111) in alkaline electrolyte was studied using in situ surface X-ray scattering techniques employing synchrotron radiation and complementary optical reflectivity and electrochemical measurements. The films are formed at pH 4 and consist of (001)-oriented hcp Co crystallites that are several nm high, a few ten nm in diameter, and remain largely unchanged after electrolyte exchange to pH 12 solution. In the pre-oxidation peak only minor changes were observed in the diffraction studies, excluding the formation of Co(OH)_2 layers. In the potential regime of Co hydroxide formation a rapid reduction of the amount of Co is observed, while the characteristic height of the islands decreases only slightly. On longer times scales, growth of 3D crystals of Co(OH)_2 occurs as well as irreversible Co dissolution into the electrolyte is found. On the basis of the structural observations oxidation of the Co film is proposed to proceed via fast formation of an ultrathin passivating layer, followed by nucleation and growth of 3D hydroxide crystals at the grain boundaries in the Co deposit.

New bonding configuration on Si(111) and Ge(111) surfaces induced by the adsorption of alkali metals

DEFF Research Database (Denmark)

Lottermoser, L.; Landemark, E.; Smilgies, D.M.

1998-01-01

The structure of the (3×1) reconstructions of the Si(111) and Ge(111) surfaces induced by adsorption of alkali metals has been determined on the basis of surface x-ray diffraction and low-energy electron diffraction measurements and density functional theory. The (3×1) surface results primarily f...... from the substrate reconstruction and shows a new bonding configuration consisting of consecutive fivefold and sixfold Si (Ge) rings in 〈11̅ 0〉 projection separated by channels containing the alkali metal atoms. © 1998 The American Physical Society...

Response of the Shockley surface state to an external electrical field: A density-functional theory study of Cu(111)

Science.gov (United States)

Berland, K.; Einstein, T. L.; Hyldgaard, P.

2012-01-01

The response of the Cu(111) Shockley surface state to an external electrical field is characterized by combining a density-functional theory calculation for a slab geometry with an analysis of the Kohn-Sham wave functions. Our analysis is facilitated by a decoupling of the Kohn-Sham states via a rotation in Hilbert space. We find that the surface state displays isotropic dispersion, quadratic until the Fermi wave vector but with a significant quartic contribution beyond. We calculate the shift in energetic position and effective mass of the surface state for an electrical field perpendicular to the Cu(111) surface; the response is linear over a broad range of field strengths. We find that charge transfer occurs beyond the outermost copper atoms and that accumulation of electrons is responsible for a quarter of the screening of the electrical field. This allows us to provide well converged determinations of the field-induced changes in the surface state for a moderate number of layers in the slab geometry.

Ballistic Electron Emission Microscopy (BEEM) of Au/Pr{sub 2}O{sub 3}/Si structures; Ballistische Elektronen Emissions Mikroskopie (BEEM) an Au/Si und Au/Pr{sub 2}O{sub 3}/Si-Strukturen

Energy Technology Data Exchange (ETDEWEB)

Mauch, I.

2007-05-15

This thesis describes Ballistic Electron Emission Microscopy (BEEM) measurements of Au/Si(111) and Au/Pr{sub 2}O{sub 3}/Si(111) structures. This technique is based on Scanning Tunnelling Microscopy (STM). It measures the ballistic transport of hot electrons through parts of the sample and across an interface, which provides a potential barrier. One part of this work was to modify the BEEM apparatus and to implement a lock in method, which modulates the tunnel current with a small frequency. In this way it is possible to study samples with very low resistance (as low as 30 k{omega}), which widely enlarges the number of samples which are appropriate for BEEM measurement at room temperature. Both types of samples studied in this thesis had low resistance and were therefore studied using the lock in method. For the classical BEEM system Au/Si(111), we observed a pronounced dependence of the sample resistance of Au/Si(111)-7 x 7 on the preparation temperature. We developed a model for the resistance of thermal prepared Au/Si(111)-7 x 7 samples. The model identifies that the low resistance is due to the surface conductivity of the reconstructed silicon surface. If the surface is prepared at a lower temperature (but still high enough that the surface is cleaned and the silicon dioxide desorbed) rough areas remain on the surface, which reduce the surface conductivity. For BEEM measurements flat areas of the sample surface are selected. The low temperature prepared samples we were able to obtain BEEM spectra as well as images at room temperature using the lock in method. The sesquioxide of praseodymium (Pr{sub 2}O{sub 3}) is currently discussed as a possible candidate for a gate oxide in semiconductor devices, since it has some of the required material properties such as a high dielectric constant, low leakage current and epitaxial growth on Si(100). We have for the first time performed BEEM measurement of praseodymium oxide. Despite a low resistance of the structures we

Au@AuPt nanoparticles embedded in B-doped graphene: A superior electrocatalyst for determination of rutin

Energy Technology Data Exchange (ETDEWEB)

Chen, Xianlan; Yang, Guangming; Feng, Shaoping; Shi, Ling; Huang, Zhaolong [School of Science, Honghe University (China); Key Laboratory of Natural Pharamaceutical & Chemical Biology of Yunnan Province Mengzi, Yunnan 661100 (China); Pan, Haibo [Fujian Key Lab of Medical Instrument & Pharmaceutical Technology, Yishan Campus, Fuzhou University, Fuzhou, Fujian 350002 (China); Liu, Wei, E-mail: liuwei4728@126.com [School of Science, Honghe University (China); Key Laboratory of Natural Pharamaceutical & Chemical Biology of Yunnan Province Mengzi, Yunnan 661100 (China)

2017-04-30

Highlights: • The formation of B-doped graphene (BG) with high content of a total B species use hydrothermal method with B{sub 2}O{sub 3} as reducing agent and boron source. • BG was exfoliated into monolayer nanosheet impregnated by Au@AuPt NPs because B atom creates a net positive charge to facilitate NPs adsorption. • The dispersed carboxyl units of BG can form hydrogen bonding with the phenolic hydroxyl groups of rutin, making more rutin participate in reaction. • Au@AuPt NPs can form charge accumulation or valence change on prominent part of the surface, improving the catalytic effect to rutin. • More electroactive sites were generated by doping B atoms into graphene structures, which act as multidimensional electron transport pathways. - Abstract: A hydrothermal approach was used to prepare B-doped graphene with B{sub 2}O{sub 3} as reductant and boron source. Results reveal that the boron atoms have been successfully embedded into graphene with a high content of a total B species (2.85 at.%). Then, B-doped graphene was exfoliated further into monolayer nanosheet by impregnating Au@AuPt core-shell nanoparticles (Au@AuPt NPs) because boron atom creates a net positive charge, which facilitates Au@AuPt NPs adsorption to form Au@AuPt NPs/B-doped graphene hybrid nanocatalysts. After that, the Au@AuPt NPs/B-doped hybrid suspension was dropped on glassy carbon electrode for sensing rutin. In this way, the dispersed carboxyl units of B-doped graphene can form hydrogen bonding with the phenolic hydroxyl groups of rutin, making rutin enrich easily on modified electrode surface to enhance the electrochemical response. At the same time, its electrochemical mechanism on the modified electrode was elucidated using cyclic voltammetry. It was found that its electrochemical behavior on modified electrode surface was a surface-controlled quasi-reversible process, and the charge transfer coefficient (α) and electron transfer number (n) were 0.296 and 2, respectively

A first-principles study of oxygen adsorption on Ir(111) surface

Energy Technology Data Exchange (ETDEWEB)

Gao, Hengjiao, E-mail: gaohengjiao@163.com; Xiong, Yuqing, E-mail: xiongyq@hotmail.com; Liu, Xiaoli, E-mail: shantianzi@126.com; Zhao, Dongcai, E-mail: zhaodongc@163.com; Feng, Yudong, E-mail: yudong_feng@sina.com; Wang, Lanxi, E-mail: wanglanxi@live.com; Wang, Jinxiao, E-mail: coldwind716@gmail.com

2016-12-15

Highlights: • Adsorption of oxygen on Ir(111) surface was studied by density functional theory. • The most stable adsorption site was determined by adsorption energy calculation. • Adsorption of oxygen at bridge and top site on Ir surface was the most stable ones. • Interaction of O 2p and Ir 5d orbits is relatively strong and formed hybridization. - Abstract: In order to understand deposition mechanism of iridium thin film by atomic layer deposition, the adsorption of oxygen on Ir(111) surface was studied by use of density functional theory and a periodical slab model. By calculating the adsorption energy and structure of oxygen at four adsorption sites (top, bridge, fcc-hollow and hcp-hollow) on Ir(111) surface, the most stable adsorption site was determined. On this basis, the banding mechanism of O and Ir atoms was studied by density of states of oxygen and iridium atoms. Oxygen adsorbed at hcp(parallel) site on Ir(111) surface was the most stable one according to the adsorption energy calculation results. Orbital charge analysis indicate that charge transferred from 5p and 5d orbit to 2p orbit of adsorbed O atoms, and 6s orbit of iridium atoms. Meanwhile, density of state study indicated that adsorption of oxygen on Ir(111) surface is mainly due to the interaction between 2p orbit of O atoms and 5d orbit of iridium atoms.

Influence of Surface Adsorption on Work Function Measurements on Gold-Platinum Interface Using Scanning Kelvin Probe Microscopy

International Nuclear Information System (INIS)

Mugo, Simon; Yuan Jun

2012-01-01

Surface potential difference (SPD) on freshly coated gold and platinum electrodes have been found to be much smaller than bulk work functions consideration and to be dependent on time. We show these discrepancies arise due to formation of surface dipoles caused by adsorbed contaminants in ambient environments. The process is reversible by gentle annealing consistent with contaminant hypothesis. Examination of potential changes on individual electrodes suggest that the Pt surface is more sensitive to ambient conditions than the Au surface in accordance with their relative chemical activities. The result has great implication for interpretation of Kelvin probe measurements obtained on practical devices exposed to ambient environments.

Spin resolved electronic transport through N@C20 fullerene molecule between Au electrodes: A first principles study

Science.gov (United States)

Caliskan, Serkan

2018-05-01

Using first principles study, through Density Functional Theory combined with Non Equilibrium Green's Function Formalism, electronic properties of endohedral N@C20 fullerene molecule joining Au electrodes (Au-N@C20) was addressed in the presence of spin property. The electronic transport behavior across the Au-N@C20 molecular junction was investigated by spin resolved transmission, density of states, molecular orbitals, differential conductance and current-voltage (I-V) characteristics. Spin asymmetric variation was clearly observed in the results due to single N atom encapsulated in the C20 fullerene cage, where the N atom played an essential role in the electronic behavior of Au-N@C20. This N@C20 based molecular bridge, exhibiting a spin dependent I-V variation, revealed a metallic behavior within the bias range from -1 V to 1 V. The induced magnetic moment, spin polarization and other relevant quantities associated with the spin resolved transport were elucidated.

The Thioacetate-Functionalized Self-Assembled Monolayers on Au: Toward High-Performance Ion-Selective Electrode for Ag{sup +}

Energy Technology Data Exchange (ETDEWEB)

Jin, Jian; Zhou, Weijie; Chen, Ying; Liu, Yilong; Sun, Xiaoqiang; Xi Haitao [Changzhou Univ., Changzhou (China)

2014-02-15

Two classes of morpholino-substituted thioacetate have been successfully synthesized and their electrochemical properties of self-assembled monolayers (SAMs) on Au electrode are measured by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The barrier property of the SAMs-modified surfaces is evaluated by using potassium ferro/ferri cyanide. The results suggest that the arenethioacetate forms higher-quality close-packed blocking monolayers in comparison with alkanethioacetate. Furthermore, it has shown that the barrier properties of these monolayers can be significantly improved by mixed SAMs formation with decanethiol. From our experimental results we find that the electron transfer reaction of [Fe(CN){sub 6}]{sup 3-/4-} redox couple occurs predominantly through the pinholes and defects present in the SAM and both SAMs show a good and fast capacity in recognition for Ag{sup +}. The morphological and elementary composition have also been examined by scanning electron microscope (SEM) and energy dispersive spectrometer (EDS)

Nonenzymatic free-cholesterol detection via a modified highly sensitive macroporous gold electrode with platinum nanoparticles.

Science.gov (United States)

Lee, Yi-Jae; Park, Jae-Yeong

2010-12-15

A sensitive macroporous Au electrode with a highly rough surface obtained through the use of with Pt nanoparticles (macroporous Au-/nPts) is reported. It has been designed for nonenzymatic free-cholesterol biosensor applications. A macroporous Au-/nPts electrode was fabricated by electroplating Pt nanoparticles onto a coral-like shaped macroporous Au electrode structure. The macroporous Au-/nPts electrode was physically characterized by field emission scanning electron microscopy (FESEM). It was confirmed that the Pt nanoparticles were well deposited on the surface of the macroporous Au electrode. The porosity and window pore size of the macroporous Au electrode were 50% and 100-300 nm, respectively. The electroplated Pt nanoparticle size was approximately 10-20 nm. Electrochemical experiments showed that the macroporous Au-/nPts exhibited a much larger surface activation area (roughness factor (RF)=2024.7) than the macroporous Au electrode (RF=46.07). The macroporous Au-/nPts also presented a much stronger electrocatalytic activity towards cholesterol oxidation than does the macroporous Au electrode. At 0.2 V, the electrode responded linearly up to a 5 mM cholesterol concentration in a neutral media, with a detection limit of 0.015 mM and detection sensitivity of 226.2 μA mM(-1) cm(-2). Meanwhile, interfering species such as ascorbic acid (AA), acetaminophen (AP), and uric acid (UA), were effectively avoided. This novel nonenzymatic detection electrode has strong applications as an electrochemically based cholesterol biosensor. Copyright © 2010 Elsevier B.V. All rights reserved.

Nitrogen adsorption on Fe(111), (100), and (110) surfaces

DEFF Research Database (Denmark)

Mortensen, Jens Jørgen; Ganduglia-Pirovano, Veronica; Hansen, Lars Bruno

1999-01-01

Adsorption energies and structures for N atoms on three low-index surfaces of Fe have been calculated using density functional theory (DFT) and the generalized gradient approximation (GGA). At low N coverage the adsorption energy on Fe(100) is found to be similar to 0.7 eV higher than on the (111......) and (110) surfaces - particularly the c(2 x 2)-N/Fe(100) structure with the N atoms in four-fold sites is very stable. We attribute the differences in adsorption energy to the lack of four-fold sites on the (111) and (110) surfaces, We suggest that at higher N coverages, islands with a structure similar...

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

Science.gov (United States)

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.

Electrochemical functionalization of Au by aminobenzene and 2-aminotoluene

International Nuclear Information System (INIS)

Rösicke, F; Neubert, T; Rappich, J; Sun, G; Hinrichs, K; Janietz, S

2016-01-01

Au surfaces are functionalized by aminobenzene (AB) and 2-aminotoluene (AT) using the electrochemical reduction of diazotized 1,4-diaminobenzene and 2,5-diaminotoluene. The IR spectroscopic measurements reveal the successful modification of Au surfaces by AB and AT. Both types of layers show similar thicknesses as obtained by microgravimetric measurements via electrochemical quartz crystal microbalance (EQCM). However, the faradaic efficiency for the grafting of AT onto an EQCM-Au sensor was 6% compared to 41% for the grafting of AB. This behavior points to a steric hindrance during the binding of AT to the EQCM surface induced by the additional methyl group present in the toluene derivative. The AB and AT functionalized surfaces have been further modified by the amidation reaction of EDC/NHS activated 4-nitrobenzoic acid. This model system reveals that the amidation reaction is slightly hindered in case of the AT layer due to the presence of the methyl group close to the amino group. This behavior leads to a four times less amount of amide bonds at the AT compared to AB modified Au surfaces as obtained from IR spectroscopic measurements. (paper)

Band selection and disentanglement using maximally localized Wannier functions: the cases of Co impurities in bulk copper and the Cu(111) surface

Energy Technology Data Exchange (ETDEWEB)

Korytar, Richard; Pruneda, Miguel; Ordejon, Pablo; Lorente, Nicolas [Centre d' Investigacio en Nanociencia i Nanotecnologia (CSIC-ICN), Campus de la UAB, E-08193 Bellaterra (Spain); Junquera, Javier, E-mail: rkorytar@cin2.e [Departamento de Ciencias de la Tierra y Fisica de la Materia Condensada, Universidad de Cantabria, E-39005 Santander (Spain)

2010-09-29

We have adapted the maximally localized Wannier function approach of Souza et al (2002 Phys. Rev. B 65 035109) to the density functional theory based SIESTA code (Soler et al 2002 J. Phys.: Condens. Mater. 14 2745) and applied it to the study of Co substitutional impurities in bulk copper as well as to the Cu(111) surface. In the Co impurity case, we have reduced the problem to the Co d-electrons and the Cu sp-band, permitting us to obtain an Anderson-like Hamiltonian from well defined density functional parameters in a fully orthonormal basis set. In order to test the quality of the Wannier approach to surfaces, we have studied the electronic structure of the Cu(111) surface by again transforming the density functional problem into the Wannier representation. An excellent description of the Shockley surface state is attained, permitting us to be confident in the application of this method to future studies of magnetic adsorbates in the presence of an extended surface state.

C6H6/Au(111): Interface dipoles, band alignment, charging energy, and van der Waals interaction

International Nuclear Information System (INIS)

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

2011-01-01

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.

Probing Surface-Adlayer Conjugation on Organic-Modified Si(111) Surfaces with Microscopy, Scattering, Spectroscopy, and Density Functional Theory

International Nuclear Information System (INIS)

Kellar, Joshua A.; Lin, Jui-Ching; Kim, Jun-Hyun; Yoder, Nathan L.; Bevan, Kirk H.; Stokes, Grace Y.; Geiger, Franz M.; Nguyen, SonBinh T.; Bedzyk, Michael J.; Hersam, Mark C.

2009-01-01

Highly conjugated molecules bound to silicon are promising candidates for organosilicon electronic devices and sensors. In this study, 1-bromo-4-ethynylbenzene was synthesized and reacted with a hydrogen-passivated Si(111) surface via ultraviolet irradiation. Through an array of characterization and modeling tools, the binding configuration and morphology of the reacted molecule were thoroughly analyzed. Atomic force microscopy confirmed an atomically flat surface morphology following reaction, while X-ray photoelectron spectroscopy verified reaction to the surface via the terminal alkyne moiety. In addition, synchrotron X-ray characterization, including X-ray reflectivity, X-ray fluorescence, and X-ray standing wave measurements, enabled sub-angstrom determination of the position of the bromine atom with respect to the silicon lattice. This structural characterization was quantitatively compared with density functional theory (DFT) calculations, thus enabling the π-conjugation of the terminal carbon atoms to be deduced. The X-ray and DFT results were additionally corroborated with the vibrational spectrum of the organic adlayer, which was measured with sum frequency generation. Overall, these results illustrate that the terminal carbon atoms in 1-bromo-4-ethynylbenzene adlayers on Si(111) retain π-conjugation, thus revealing alkyne molecules as promising candidates for organosilicon electronics and sensing.

High-temperature morphology of stepped gold surfaces

International Nuclear Information System (INIS)

Bilalbegovic, G.; Tosatti, E.; Ercolessi, F.

1992-04-01

Molecular dynamics simulations with a classical many-body potential are used to study the high-temperature stability of stepped non-melting metal surfaces. We have studied in particular the Au(111) vicinal surfaces in the (M+1, M-1, M) family and the Au(100) vicinals in the (M, 1, 1) family. Some vicinal orientations close to the non-melting Au(111) surface become unstable close to the bulk melting temperature and facet into a mixture of crystalline (111) regions and localized surface-melted regions. On the contrary, we do not find high-temperature faceting for vicinals close to Au(100), also a non-melting surface. These (100) vicinal surfaces gradually disorder with disappearance of individual steps well below the bulk melting temperature. We have also studied the high-temperature stability of ledges formed by pairs of monoatomic steps of opposite sign on the Au(111) surface. It is found that these ledges attract each other, so that several of them merge into one larger ledge, whose edge steps then act as a nucleation site for surface melting. (author). 43 refs, 8 figs

High-Quality AZO/Au/AZO Sandwich Film with Ultralow Optical Loss and Resistivity for Transparent Flexible Electrodes.

Science.gov (United States)

Zhou, Hua; Xie, Jing; Mai, Manfang; Wang, Jing; Shen, Xiangqian; Wang, Shuying; Zhang, Lihua; Kisslinger, Kim; Wang, Hui-Qiong; Zhang, Jinxing; Li, Yu; Deng, Junhong; Ke, Shanming; Zeng, Xierong

2018-05-09

Transparent flexible electrodes are in ever-growing demand for modern stretchable optoelectronic devices, such as display technologies, solar cells, and smart windows. Such sandwich-film-electrodes deposited on polymer substrates are unattainable because of the low quality of the films, inducing a relatively large optical loss and resistivity as well as a difficulty in elucidating the interference behavior of light. In this article, we report a high-quality AZO/Au/AZO sandwich film with excellent optoelectronic performance, e.g., an average transmittance of about 81.7% (including the substrate contribution) over the visible range, a sheet resistance of 5 Ω/sq, and a figure-of-merit (FoM) factor of ∼55.1. These values are well ahead of those previously reported for sandwich-film-electrodes. Additionally, the interference behaviors of light modulated by the coat and metal layers have been explored with the employment of transmittance spectra and numerical simulations. In particular, a heater device based on an AZO/Au/AZO sandwich film exhibits high performance such as short response time (∼5 s) and uniform temperature field. This work provides a deep insight into the improvement of the film quality of the sandwich electrodes and the design of high-performance transparent flexible devices by the application of a flexible substrate with an atomically smooth surface.

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

Energy Technology Data Exchange (ETDEWEB)

Golibrzuch, Kai; Shirhatti, Pranav R.; Kandratsenka, Alexander; Wodtke, Alec M.; Bartels, Christof [Institute for Physical Chemistry, Georg August University of Göttingen, Göttingen 37077 (Germany); Max Planck Institute for Biophysical Chemistry, Göttingen 37077 (Germany); Rahinov, Igor [Department of Natural Sciences, The Open University of Israel, Ra' anana 4353701 (Israel); Auerbach, Daniel J. [Institute for Physical Chemistry, Georg August University of Göttingen, Göttingen 37077 (Germany); Max Planck Institute for Biophysical Chemistry, Göttingen 37077 (Germany); Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106 (United States)

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.

Excited-State N2 Dissociation Pathway on Fe-Functionalized Au.

Science.gov (United States)

Martirez, John Mark P; Carter, Emily A

2017-03-29

Localized surface plasmon resonances (LSPRs) offer the possibility of light-activated chemical catalysis on surfaces of strongly plasmonic metal nanoparticles. This technology relies on lower-barrier bond formation and/or dissociation routes made available through energy transfer following the eventual decay of LSPRs. The coupling between these decay processes and a chemical trajectory (nuclear motion, charge-transfer, intersystem crossing, etc.) dictates the availability of these alternative (possibly lower barrier) excited-state channels. The Haber-Bosch method of NH 3 synthesis from N 2 and H 2 is notoriously energy intensive. This is due to the difficulty of N 2 dissociation despite the overall reaction being thermodynamically favorable at ambient temperatures and pressures. LSPRs may provide means to improve the kinetics of N 2 dissociation via induced resonance electronic excitation. In this work, we calculate, via embedded n-electron valence second-order perturbation theory within the density functional embedding theory, the excited-state potential energy surfaces for dissociation of N 2 on an Fe-doped Au(111) surface. This metal alloy may take advantage simultaneously of the strong LSPR of Au and the catalytic activity of Fe toward N 2 dissociation. We find the ground-state dissociation activation energy to be 4.74 eV/N 2 , with Fe as the active site on the surface. Consecutive resonance energy transfers (RETs) may be accessed due to the availability of many electronically excited states with intermediate energies arising from the metal surface that may couple to states induced by the Fe-dopant and the adsorbate molecule, and crossing between excited states may effectively lower the dissociation barrier to 1.33 eV. Our work illustrates that large energetic barriers, prohibitive toward chemical reaction, may be overcome through multiple RETs facilitating an otherwise difficult chemical process.

Large-scale, Lithography-free Production of Transparent Nanostructured Surface for Dual-functional Electrochemical and SERS Sensing

DEFF Research Database (Denmark)

Sanger, Kuldeep; Durucan, Onur; Wu, Kaiyu

2017-01-01

aspect ratios distributed homogeneously on a 4-inch fused silica wafer. The sensor was made up of three-electrode array, obtained by subsequent e-beam evaporation of Au on nanostructures in selected areas through a shadow mask. The SERS performance was evaluated through surface-averaged enhancement......-reversible behavior with decrease in peak potential separation (∆Ep ~90mV) and higher peak currents (Ipa/Ipc ~1), comparing to planar electrodes (∆Ep ~560mV). The oxidation potential of PAR was also lowered by ~80 mV on nanostructured electrodes. To illustrate dual-functional sensing, quantitative evaluation of PAR...

Self-assembled gold nanoparticles modified ITO electrodes: The monolayer binder molecule effect

Energy Technology Data Exchange (ETDEWEB)

Ballarin, Barbara; Cassani, Maria Cristina; Scavetta, Erika; Tonelli, Domenica [Dipartimento di Chimica Fisica ed Inorganica, Universita di Bologna, V.le Risorgimento 4, 40136 Bologna, INSTM, UdR Bologna (Italy)

2008-11-15

The fabrication of gold attached organosilane-coated indium tin oxide Au{sub NPs}-MPTMS/ITO and Au{sub NPs}-APTES/ITO electrodes [MPTMS 3-(mercaptopropyl)-trimethoxysilane, APTES = 3-(aminopropyl)-triethoxysilane, ITO = indium tin oxide] was carried out making use of a well-known two-step procedure and the role played by the -SH and -NH{sub 2} functional groups in the two electrodes has been examined and compared using different techniques. Information about particle coverage and inter-particle spacing has been obtained using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM) whereas, bulk surface properties have been probed with UV-vis spectroscopy, CV and electrochemical impedance spectroscopy (EIS). The catalytic activity of the two electrodes has been evaluated studying the electrooxidation of methanol in alkaline conditions. The results obtained show that the NH{sub 2} functionality in the APTES binder molecule favours the formation of isle-like Au nanoparticle aggregates that lead to both a higher electron transfer and electrocatalytic activity. (author)

Electrochemical Determination of Food Preservative Nitrite with Gold Nanoparticles/p-Aminothiophenol-Modified Gold Electrode.

Science.gov (United States)

Üzer, Ayşem; Sağlam, Şener; Can, Ziya; Erçağ, Erol; Apak, Reşat

2016-08-02

Due to the negative impact of nitrate and nitrite on human health, their presence exceeding acceptable levels is not desired in foodstuffs. Thus, nitrite determination at low concentrations is a major challenge in electroanalytical chemistry, which can be achieved by fast, cheap, and safe electrochemical sensors. In this work, the working electrode (Au) was functionalized with p-aminothiophenol (p-ATP) and modified with gold nanoparticles (Au-NPs) to manufacture the final (Au/p-ATP-Aunano) electrode in a two-step procedure. In the first step, p-ATP was electropolymerized on the electrode surface to obtain a polyaminothiophenol (PATP) coating. In the second step, Au/p-ATP-Aunano working electrode was prepared by coating the surface with the use of HAuCl₄ solution and cyclic voltammetry. Determination of aqueous nitrite samples was performed with the proposed electrode (Au/p-ATP-Aunano) using square wave voltammetry (SWV) in pH 4 buffer medium. Characteristic peak potential of nitrite samples was 0.76 V, and linear calibration curves of current intensity versus concentration was linear in the range of 0.5-50 mg·L(-1) nitrite with a limit of detection (LOD) of 0.12 mg·L(-1). Alternatively, nitrite in sausage samples could be colorimetrically determined with high sensitivity by means of p-ATP‒modified gold nanoparticles (AuNPs) and naphthylethylene diamine as coupling agents for azo-dye formation due to enhanced charge-transfer interactions with the AuNPs surface. The slopes of the calibration lines in pure NO₂(-) solution and in sausage sample solution, to which different concentrations of NO₂(-) standards were added, were not significantly different from each other, confirming the robustness and interference tolerance of the method. The proposed voltammetric sensing method was validated against the colorimetric nanosensing method in sausage samples.

Electrochemical Sensing of Neurotoxic Agents Based on Their Electron Transfer Promotion Effect on an Au Electrode.

Science.gov (United States)

Shimada, Hiroshi; Noguchi, Shiori; Yamamoto, Masahiro; Nishiyama, Katsuhiko; Kitamura, Yusuke; Ihara, Toshihiro

2017-06-06

An electrochemical molecular sensor based on a new principle is reported. Nereistoxin (NRT, 4-N,N-dimethylamino-1,2-dithiolane), a naturally occurring neurotoxin (nicotinic acetylcholine receptor agonist), was adsorbed on an Au electrode via Au-S covalent bonding and accelerated the electron transfer between the electrode and the marker, ferricyanide anion. The contrast between the electrochemical responses obtained with the bare and NRT-modified Au electrodes was more pronounced at a low ionic strength of the supporting electrolyte, KCl. In the presence of 1 mM KCl, almost a 0/1 contrast between the signals was obtained through electrostatic interaction between the protonated tertiary amino group of NRT and the anionic ferricyanide ion. No current was observed with an electrode modified with mercaptopropionic acid. An unusually low ionic strength thickened the electric double layer to the degree where current was not observed with the bare electrode. The effect of the electrostatic concentration of the marker ion becomes obvious under such conditions. Commercially available NRT-related pesticides such as Cartap and Bensultap were also detected using the same format after pretreatments by hydrolysis/reduction. The present sensing method was successfully applied to human serum with satisfactory sensitivity.

Au@MnO2 core-shell nanomesh electrodes for transparent flexible supercapacitors.

Science.gov (United States)

Qiu, Tengfei; Luo, Bin; Giersig, Michael; Akinoglu, Eser Metin; Hao, Long; Wang, Xiangjun; Shi, Lin; Jin, Meihua; Zhi, Linjie

2014-10-29

A novel Au@MnO2 supercapacitor is presented. The sophisticated core-shell architecture combining an Au nanomesh core with a MnO2 shell on a flexible polymeric substrate is demonstrated as an electrode for high performance transparent flexible supercapacitors (TFSCs). Due to their unique structure, high areal/gravimetric capacitance and rate capability for TFSCs are achieved. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Label-Free Impedance Sensing of Aflatoxin B1 with Polyaniline Nanofibers/Au Nanoparticle Electrode Array

Directory of Open Access Journals (Sweden)

Ajay Kumar Yagati

2018-04-01

Full Text Available Aflatoxin B1 (AFB1 is produced by the Aspergillus flavus and Aspergillus parasiticus group of fungi which is most hepatotoxic and hepatocarcinogenic and occurs as a contaminant in a variety of foods. AFB1 is mutagenic, teratogenic, and causes immunosuppression in animals and is mostly found in peanuts, corn, and food grains. Therefore, novel methodologies of sensitive and expedient strategy are often required to detect mycotoxins at the lowest level. Herein, we report an electrochemical impedance sensor that selectively detects AFB1 at the lowest level by utilizing polyaniline nanofibers (PANI coated with gold (Au nanoparticles composite based indium tin oxide (ITO disk electrodes. The Au-PANI nanocomposites were characterized by scanning electron microscopy (SEM, X-ray diffraction (XRD spectroscopy, and electrochemical impedance spectroscopy (EIS. The composite electrode exhibited a 14-fold decrement in |Z|1 Hz in comparison with the bare electrode. The Au-PANI acted as an effective sensing platform having high surface area, electrochemical conductivity, and biocompatibility which enabled greater loading deposits of capture antibodies. As a result, the presence of AFB1 was screened with high sensitivity and stability by monitoring the changes in impedance magnitude (|Z| in the presence of a standard iron probe which was target specific and proportional to logarithmic AFB1 concentrations (CAFB1. The sensor exhibits a linear range 0.1 to 100 ng/mL with a detection limit (3σ of 0.05 ng/mL and possesses good reproducibility and high selectivity against another fungal mycotoxin, Ochratoxin A (OTA. With regard to the practicability, the proposed sensor was successfully applied to spiked corn samples and proved excellent potential for AFB1 detection and development of point-of-care (POC disease sensing applications.

X-ray photoelectron spectroscopy studies of aging effects on the surface of Au - a-Si:H - Sb-Cr Schottky diodes

International Nuclear Information System (INIS)

Paquin, L.; Wertheimer, M.R.; Sacher, E.; McIntyre, N.S.

1989-01-01

During investigations of Au - a-Si:H - Cr-Sb photovoltaic Schottky diodes, it was observed that photoconversion parameters (I sc ,, V oc , η), improved markedly with time for samples stored for several weeks in ambient air. This was always accompanied by apparent color changes in the area under the top (Au) electrode, from gold to deep purple, and by evolution of its surface conductivity σ from a highly conducting to an insulating state. Profilometry indicated that the colored area rose about 80 nm above the original surface during these changes. These diodes have been examined using depth-profiling surface analytical techniques, namely secondary-ion mass spectroscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy (XPS), but primarily the latter. The XPS studies of the entire layer thickness on the gold electrode were carried out using erosion by Ar + ion bombardment. The XPS line positions were used to infer electrical properties of silicon and gold constituents. The results show that Si atoms first diffuse through the gold electrode, where they react with atmospheric constituents to form a thick layer composed mainly of SiO 2 . this layer is responsible for the observed changes in color, σ, and I sc . The latter change, which leads to a maximum rise in η of about 60%, is felt to result from the fact that the SiO 2 layer acts as an antireflection coating. Gold from the electrode layer also diffuses outward, mixed intimately with the silicon oxide. Further aging results in a degradation of the electrical continuity of the Au electrode, which is believed to be responsible for the observed slow drop in σ. (author). 14 refs., 9 figs

Amperometric carbohydrate antigen 19-9 immunosensor based on three dimensional ordered macroporous magnetic Au film coupling direct electrochemistry of horseradish peroxidase

Energy Technology Data Exchange (ETDEWEB)

Zhang, Qi [College of Sciences, Nanjing Tech University, Nanjing 211816 (China); Chen, Xiaojun, E-mail: chenxj_njut@126.com [College of Sciences, Nanjing Tech University, Nanjing 211816 (China); State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009 (China); Tang, Yin [Zhangjiagang Hospital of Traditional Chinese Medicine, Zhangjiagang 215600 (China); Ge, Lingna; Guo, Buhua [College of Sciences, Nanjing Tech University, Nanjing 211816 (China); Yao, Cheng, E-mail: yaochengnjut@163.com [College of Sciences, Nanjing Tech University, Nanjing 211816 (China)

2014-03-01

Highlights: • Three dimensional ordered macroporous magnetic electrode was newly used in electrochemical immunosensor. • The large surface area of macroporous magnetic electrode could improve the immobilized amount of antibody. • Au nanoparticles functionalized SBA-15 was used to immobilize enzyme labeled Ab₂ and enzyme. • Macroporous magnetic electrode and Au nanoparticles composite facilitated the direct electron transfer of enzyme. • The immunoassay avoided adding electron transfer mediator, simplifying the procedure. Abstract: A sandwich-type electrochemical immunosensor for the detection of carbohydrate antigen 19-9 (CA 19-9) antigen based on the immobilization of primary antibody (Ab₁) on three dimensional ordered macroporous magnetic (3DOMM) electrode, and the direct electrochemistry of horseradish peroxidase (HRP) that was used as both the label of secondary antibody (Ab₂) and the blocking reagent. The 3DOMM electrode was fabricated by introducing core–shell Au–SiO₂@Fe₃O₄ nanospheres onto the surface of three dimensional ordered macroporous (3DOM) Au electrode via the application of an external magnet. Au nanoparticles functionalized SBA-15 (Au@SBA-15) was conjugated to the HRP labeled secondary antibody (HRP-Ab₂) through the Au–SH or Au–NH₃⁺ interaction, and HRP was also used as the block reagent. The formation of antigen–antibody complex made the combination of Au@SBA-15 and 3DOMM exhibit remarkable synergistic effects for accelerating direct electron transfer (DET) between HRP and the electrode. Under the optimal conditions, the DET current signal increased proportionally to CA 19-9 concentration in the range of 0.05 to 15.65 U mL⁻¹ with a detection limit of 0.01 U mL⁻¹. Moreover, the immunosensor showed high selectivity, good stability, satisfactory reproducibility and regeneration. Importantly, the developed method was used to assay clinical serum specimens, achieving a good relation with those obtained from

First-Principles Studies of Functionalized Si(111) in Air and in Water

Science.gov (United States)

Li, Yan; Galli, Giulia

2011-03-01

We have investigated structural, electronic and vibrational properties of hydrogen and methyl-terminated Si(111) surfaces both in air and in contact with water, by combining density functional theory and many-body perturbation theory within the GW approximations. The computed surface dipole moments for both H-Si(111) and CH3-Si(111) surfaces were found to be consistent with measured electron affinities (EAs), and can be explain by simple electronegative trends. While GW self-energy corrections greatly improve the absolute values of EAs, the EA difference of the two surfaces remains overestimated by about 0.3 eV. The variations in CH3 frequencies, e.g. the umbrella mode and CH stretching mode, for the surface in air and water are also well reproduced by our calculations. The influence exerted by the adsorption of water molecules on the hydrophobic H-Si(111) and CH3-(111) surfaces, in particular, on the EAs and the surface vibrational frequencies will be discussed and compared with recent experiments. This work was funded by NSF under Grant No. CHE-0802907.

Symposium Supramolecular Assemblies on Surface: Nanopatterning, Functionality and Reactivity

Science.gov (United States)

2016-05-19

formed and we relate these observations to recent reports of de- wetting of C60 on alkali halide surfaces. The hBN flakes, which are prepared by... annealing will be discussed while for dicarbonitrile polyphenyl derivatives the adsorption behavior on Au(111) will be compared to the one on graphene

The interfacial capacitance of an oxidised polycrystalline gold electrode in an aqueous HClO4 electrolyte

International Nuclear Information System (INIS)

Grdeń, M.

2013-01-01

The interfacial capacitance of a polycrystalline gold electrode electrochemically oxidised in an aqueous 0.1 M HClO 4 electrolyte has been investigated by means of the electrochemical impedance spectroscopy. From 1.3 to 3 monolayers of Au atoms were oxidised under constant potential conditions and for various oxidation times. The capacitance of the oxidised layers was analysed as a function of the electrode potential and the extent of the surface oxidation. It was found that the interfacial capacitance decreases upon surface oxidation. The components of the interfacial capacitance of the oxidised layer: the double layer capacitance and the capacitance of the oxidised layer; have been separated. The capacitance of the double layer of the oxidised surface was found to be comparable to the capacitance measured for the metallic surface. - Highlights: • The impedance spectra for thin layers of Au oxides/hydroxides were acquired. • Separate determination of the double layer and the oxide capacitances of oxidised Au • The double layer capacitances of oxidised and non-oxidised Au surfaces are comparable

Bonding and orientation of 1,4-benzenedimethanethiol on Au(111) prepared from solution and from gas phase

International Nuclear Information System (INIS)

Pasquali, L; Terzi, F; Zanardi, C; Seeber, R; Paolicelli, G; Mahne, N; Nannarone, S

2007-01-01

The orientation and bonding of 1,4-benzenedimethanethiol molecules on Au(111) is studied by means of x-ray and ultraviolet (UV) photoemission, x-ray absorption and metastable deexcitation spectroscopy. The organic films are prepared both from solution and by exposing the clean substrate to the vapours of the substance in an evacuated environment. This leads to two different growth modes: when self-assembled monolayers (SAMs) are prepared from solution, the molecules tend to form a bilayer film with the molecules standing upright and with the molecular axis forming an angle of about 30 0 with respect to the substrate normal; when growth is carried out from the gas phase, the molecules tend to assume at the earliest stages of exposure a flat-lying configuration, with both sulfur end-groups bonding to Au; at increasing exposure the surface coverage presents a saturation and the chemisorbed molecules tend to assume an upright arrangement

Selection of conformational states in surface self-assembly for a molecule with eight possible pairs of surface enantiomers

DEFF Research Database (Denmark)

Nuermaimaiti, Ajiguli; Schultz-Falk, Vickie; Lind Cramer, Jacob

2016-01-01

Self-assembly of a molecule with many distinct conformational states, resulting in eight possible pairs of surface enantiomers, is investigated on a Au(111) surface under UHV conditions. The complex molecule is equipped with alkyl and carboxyl moieties to promote controlled self-assembly of lamel......Self-assembly of a molecule with many distinct conformational states, resulting in eight possible pairs of surface enantiomers, is investigated on a Au(111) surface under UHV conditions. The complex molecule is equipped with alkyl and carboxyl moieties to promote controlled self......-assembly of lamellae structures. From statistical analysis of Scanning Tunnelling Microscopy (STM) data we observe a clear selection of specific conformational states after self-assembly. Using Density Functional Theory (DFT) calculations we rationalise how this selection is correlated to the orientation of the alkyl...

Comparative study on hydrogenation of propanal on Ni(111) and Cu(111) from density functional theory

Energy Technology Data Exchange (ETDEWEB)

An, Wei, E-mail: weian@sues.edu.cn; Men, Yong; Wang, Jinguo

2017-02-01

Highlights: • Hydrogenation of propanal is kinetically much faster on Ni(111) than Cu(111). • Hydroxyl route is prefered over alkoxy route on Ni(111). • Alkoxy route is prefered over hydroxyl route on Cu(111). • Activation barrier for hydrogenation of carbonyl is lowered by H-tunneling effect. • η{sup 2}(C,O)-adsorption mode is beneficial for hydrogenation/dehydrogenation of aldehyde. - Abstract: Using propanal as a probe molecule, we have comparatively investigated hydrogenation of carbonyl (C=O) in short carbon-chain aldehyde on Ni(111) and Cu(111) by means of periodic density functional theory. Our focus is in particular on the differentiation of reaction route in sequential hydrogenation on Ni(111) and Cu(111) following Langmuir–Hinshelwood mechanism. Strong binding with alkoxy intermediates has great impact on altering reaction pathways on the two surfaces, where hydroxyl route via 1-hydroxyl propyl intermediate is dominant on Ni(111), but alkoxy route via propoxyl intermediate is more likely on Cu(111) due to a higher activiation barrier of initial hydrogenation in hydroxyl route. In comparison, hydrogenation of carbonyl on Ni(111) is kinetically much faster than that on Cu(111) as a result of much lower activation barrier in rate-determining step (i.e., 13.2 vs 26.8 kcal/mol) of most favorable reaction pathways. Furthermore, the discrepancy in calculated and experimental barriers can be well explained by using the concept of H-tunneling effect on bond forming with H atoms during sequential hydrogenation. The different features of electronic structure exhibited by the two metal surfaces provide insight into their catalytic behaviors.

Electrochemical noise and impedance of Au electrode/electrolyte interfaces enabling extracellular detection of glioma cell populations.

Science.gov (United States)

Rocha, Paulo R F; Schlett, Paul; Kintzel, Ulrike; Mailänder, Volker; Vandamme, Lode K J; Zeck, Gunther; Gomes, Henrique L; Biscarini, Fabio; de Leeuw, Dago M

2016-10-06

Microelectrode arrays (MEA) record extracellular local field potentials of cells adhered to the electrodes. A disadvantage is the limited signal-to-noise ratio. The state-of-the-art background noise level is about 10 μVpp. Furthermore, in MEAs low frequency events are filtered out. Here, we quantitatively analyze Au electrode/electrolyte interfaces with impedance spectroscopy and noise measurements. The equivalent circuit is the charge transfer resistance in parallel with a constant phase element that describes the double layer capacitance, in series with a spreading resistance. This equivalent circuit leads to a Maxwell-Wagner relaxation frequency, the value of which is determined as a function of electrode area and molarity of an aqueous KCl electrolyte solution. The electrochemical voltage and current noise is measured as a function of electrode area and frequency and follow unambiguously from the measured impedance. By using large area electrodes the noise floor can be as low as 0.3 μVpp. The resulting high sensitivity is demonstrated by the extracellular detection of C6 glioma cell populations. Their minute electrical activity can be clearly detected at a frequency below about 10 Hz, which shows that the methodology can be used to monitor slow cooperative biological signals in cell populations.

A density functional theory study on the conversion of ethylene to carbon monomer on PdAu(1 0 0) surface

Energy Technology Data Exchange (ETDEWEB)

Zhang, Minhua; Yang, Bing [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin 300072 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Yu, Yingzhe, E-mail: yzhyu@tju.edu.cn [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin 300072 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China)

2015-11-30

Graphical abstract: - Highlights: • The successive decomposition of ethylene on PdAu(1 0 0) was studied with DFT method. • The C−H, C−C bond scission and a hydrogen-shift process were investigated. • The alloying of Au with Pd affects the studied reactions on PdAu(1 0 0) greatly. - Abstract: Calculations based on the first-principles density functional theory (DFT) were performed to study the possible transformation pathways of ethylene on PdAu(1 0 0) surface to investigate the effect of Au atom alloying with Pd on the formation of CHx (x = 0–2), which may eventually form carbon monomer and lead to the deactivation of catalysts. The energetic properties of reactions including the scission of the C−H, C−C bond and a hydrogen-shift process were determined. The C−H bond scission is confirmed to be prone to happen on the studied surface, while it is difficult for the C−C bond scission to occur due to relatively high barriers, the values of which are as high as 2.72–4.62 eV. The activation barriers for all related reactions except for the dehydrogenation of vinyl, vinylidene and acetenyl demonstrate that it is harder for the conversion of ethylene to occur on PdAu(1 0 0) surface than on Pd(1 0 0) surface, especially for the C−C bond scission. All the results indicate that the alloying of Au atom with pure Pd catalyst can prevent the formation of carbon monomer, which may notably affect properties of catalysts.

Doped graphene electrodes for organic solar cells

International Nuclear Information System (INIS)

Park, Hyesung; Kim, Ki Kang; Bulovic, Vladimir; Kong, Jing; Rowehl, Jill A

2010-01-01

In this work graphene sheets grown by chemical vapor deposition (CVD) with controlled numbers of layers were used as transparent electrodes in organic photovoltaic (OPV) devices. It was found that for devices with pristine graphene electrodes, the power conversion efficiency (PCE) is comparable to their counterparts with indium tin oxide (ITO) electrodes. Nevertheless, the chances for failure in OPVs with pristine graphene electrodes are higher than for those with ITO electrodes, due to the surface wetting challenge between the hole-transporting layer and the graphene electrodes. Various alternative routes were investigated and it was found that AuCl 3 doping on graphene can alter the graphene surface wetting properties such that a uniform coating of the hole-transporting layer can be achieved and device success rate can be increased. Furthermore, the doping both improves the conductivity and shifts the work function of the graphene electrode, resulting in improved overall PCE performance of the OPV devices. This work brings us one step further toward the future use of graphene transparent electrodes as a replacement for ITO.

Electrical conductivity dependence of thin metallic films of Au and Pd as a top electrode in capacitor applications

International Nuclear Information System (INIS)

Nazarpour, S.; Langenberg, E.; Jambois, O.; Ferrater, C.; Garcia-Cuenca, M.V.; Polo, M.C.; Varela, M.

2009-01-01

Electrical conductivity dependence of thin metallic films of Au and Pd over the different perovskites was investigated. It is found from electrical properties that crystallographic growth orientation of Au and Pd thin layers attained from X-ray diffraction results indicate the slop of current (I)-voltage (V) plots. Besides, surface morphology and topography was considered using Field Emission Scanning Electron Microscopy and Atomic Force Microscopy, respectively. Obtained results showed the Stranski-Krastanov growth of the Pd and Au. Indeed, diminishing of the root-mean-square roughness of Pd/BiMnO 3 /SrTiO 3 following by Au deposition should be concerned due to growth of Au onto the crack-like parts of the substrate. These crack-like parts appeared due to parasitic phases of the Bi-Mn-O system mainly Mn 3 O 4 (l 0 l) and Mn 3 O 4 (0 0 4 l). The different response in the electrical properties of heterostructures suggests that electrical conductance of the Au and Pd thin metallic films have the crystallographic orientation dependence. Furthermore, polycrystallinity of the thin metallic films are desired in electrode applications due to increase the conductivity of the metallic layers.

Low-Temperature Preparation of (111)-oriented Pb(Zr,Ti)O3 Films Using Lattice-Matched (111)SrRuO3/Pt Bottom Electrode by Metal-Organic Chemical Vapor Deposition

Science.gov (United States)

Kuwabara, Hiroki; Sumi, Akihiro; Okamoto, Shoji; Hoko, Hiromasa; Cross, Jeffrey S.; Funakubo, Hiroshi

2009-04-01

Pb(Zr0.35Ti0.65)O3 (PZT) films 170 nm thick were prepared at 415 °C by pulsed metal-organic chemical vapor deposition. The (111)-oriented PZT films with local epitaxial growth were obtained on (111)SrRuO3/(111)Pt/TiO2/SiO2/Si substrates and their ferroelectricities were ascertained. Ferroelectricity was improved by postannealing under O2 gas flow up to 550 °C. Larger remanent polarization and better fatigue endurance were obtained using a SrRuO3 top electrode compared to a Pt top electrode for PZT films after annealing at 500 °C.

A facile approach for reducing the working voltage of Au/TiO2/Au nanostructured memristors by enhancing the local electric field

Science.gov (United States)

Arab Bafrani, Hamidreza; Ebrahimi, Mahdi; Bagheri Shouraki, Saeed; Moshfegh, Alireza Z.

2018-01-01

Memristor devices have attracted tremendous interest due to different applications ranging from nonvolatile data storage to neuromorphic computing units. Exploring the role of surface roughness of the bottom electrode (BE)/active layer interface provides useful guidelines for the optimization of the memristor switching performance. This study focuses on the effect of surface roughness of the BE electrode on the switching characteristics of Au/TiO2/Au three-layer memristor devices. An optimized wet-etching treatment condition was found to modify the surface roughness of the Au BE where the measurement results indicate that the roughness of the Au BE is affected by both duration time and solution concentrations of the wet-etching process. Then we fabricated arrays of TiO2-based nanostructured memristors sandwiched between two sets of cross-bar Au electrode lines (junction area 900 μm2). The results revealed a reduction in the working voltages in current-voltage characteristic of the device performance when increasing the surface roughness at the Au(BE)/TiO2 active layer interface. The set voltage of the device (Vset) significantly decreased from 2.26-1.93 V when we increased the interface roughness from 4.2-13.1 nm. The present work provides information for better understanding the switching mechanism of titanium-dioxide-based devices, and it can be inferred that enhancing the roughness of the Au BE/TiO2 active layer interface leads to a localized non-uniform electric field distribution that plays a vital role in reducing the energy consumption of the device.

Electrochemical fabrication of clean dendritic Au supported Pt clusters for electrocatalytic oxidation of formic acid

International Nuclear Information System (INIS)

Xia Yue; Liu Jun; Huang Wei; Li Zelin

2012-01-01

Highlights: ► A smooth Au surface was rebuilt into clean dendrite via square wave potential pulses. ► It was performed in blank H 2 SO 4 solution without Au(III) species and other additives. ► Dendritic Au provided certain advantage for dispersing Pt due to its unique structure. ► Pt-decorated dendritic Au demonstrated high activity for the HCOOH electrooxidation. - Abstract: We report here the fabrication of clean dendritic gold (DG) directly on a smooth Au electrode via square wave potential pulses (SWPPs) in a blank H 2 SO 4 solution containing no Au(III) species and additives. The effects of potential range, frequency and duration time of SWPPs and H 2 SO 4 concentration on the construction of DG were systematically investigated. A possible mechanism was proposed to explain the growth of DG. The whole process was templateless and surfactantless, and therefore effectively avoided possible contaminations that occurred in other synthetic routes. Further, the prepared DG electrode functioned as a scaffold to support electrodeposited Pt clusters, producing Pt-decorated DG (Pt-DG) electrodes. The electrocatalytic properties of Pt-DG electrodes with various Pt loadings were examined for the oxidation of formic acid. The low Pt loading Pt-DG demonstrated different electrochemical behavior from that on Pt-decorated smooth gold (Pt-SG) and on Pt-decorated gold nanoparticles because there were more defect sites like steps and edges on the DG surface. Ensemble effect, as well as electronic effect, accounts for the improved electrocatalytic activity of low Pt loading Pt-DG.

Growth and structure of Co/Au magnetic thin films; Croissance et structure des couches minces magnetiques Co/Au

Energy Technology Data Exchange (ETDEWEB)

Marsot, N

1999-01-14

We have studied the growth and the crystallographic structure of magnetic ultra thin cobalt/gold films (Co/Au), in order to investigate the correlations between their magnetic and structural properties. Room temperature (R.T.) Co growth on Au (111) proceeds in three stages. Up to 2 Co monolayers (ML), a bilayer island growth mode is observed. Between 2 and 5 ML, coalescence of the islands occurs, covering the substrate surface and a Co/Au mixing is observed resulting from the de-construction of the Herringbone reconstruction. Finally, beyond 5 ML, the CoAu mixing is buried and the Co growth continues in a 3-D growth. Annealing studies at 600 K on this system show a smoothing effect of the Co film, and at the same time, segregation of Au atoms. The quality of the Co/Au interface (sharpness) is not enhanced by the annealing. The local order was studied by SEXAFS and the long range order by GIXRD showing that the Co film has a hexagonal close packed structure, with an easy magnetization axis perpendicular to the surface. From a local order point of view, the Co grows with an incoherent epitaxy and keeps its own bulk parameters. The GIXRD analysis shows a residual strain in the Co film of 4%. The difference observed between the local order analysis and the long range order results is explained in terms of the low dimensions of the diffracting domains. The evolution of film strains, as a function of the Co coverage, shows a marked deviation from the elastic strain theory. Modification of the strain field in the Co film as a function of the Au coverage is studied by GIXRD analysis. The Au growth study, at R.T., shows no evidence of a Au/Co mixing in the case of the Au/Co interface. The Au overlayer adopts a twinned face centred cubic structure on the rough Co film surface. (author)

Electrocatalytic oxidation of ascorbic acid using a single layer of gold nanoparticles immobilized on 1,6-hexanedithiol modified gold electrode

International Nuclear Information System (INIS)

Sivanesan, A.; Kannan, P.; Abraham John, S.

2007-01-01

This paper describes the electrocatalytic oxidation of ascorbic acid (AA) in phosphate buffer solution by the immobilized citrate capped gold nanoparticles (AuNPs) on 1,6-hexanedithiol (HDT) modified Au electrode. X-ray photoelectron spectrum (XPS) of HDT suggests that it forms a monolayer on Au surface through one of the two -SH groups and the other -SH group is pointing away from the electrode surface. The free -SH groups of HDT were used to covalently attach colloidal AuNPs. The covalent attachment of AuNPs on HDT monolayer was confirmed from the observed characteristic carboxylate ion stretching modes of citrate attached with AuNPs in the infra-red reflection absorption spectrum (IRRAS) in addition to a higher reductive desorption charges obtained for AuNPs immobilized on HDT modified Au (Au/HDT/AuNPs) electrode in 0.1 M KOH when compared to HDT modified Au (Au/HDT) electrode. The electron transfer reaction of [Fe(CN) 6 ] 4-/3- was markedly hindered at the HDT modified Au (Au/HDT) electrode while it was restored with a peak separation of 74 mV after the immobilization of AuNPs on Au/HDT (Au/HDT/AuNPs) electrode indicating a good electronic communication between the immobilized AuNPs and the underlying bulk Au electrode through a HDT monolayer. The Cottrell slope obtained from the potential-step chronoamperometric measurements for the reduction of ferricyanide at Au/HDT/AuNPs was higher than that of bare Au electrode indicating the increased effective surface area of AuNPs modified electrode. The Au/HDT/AuNPs electrode exhibits excellent electrocatalytic activity towards the oxidation of ascorbic acid (AA) by enhancing the oxidation peak current to more than two times with a 210 mV negative shift in the oxidation potential when compared to a bare Au electrode. The standard heterogeneous electron transfer rate constant (k s ) calculated for AA oxidation at Au/HDT/AuNPs electrode was 5.4 x 10 -3 cm s -1 . The oxidation peak of AA at Au/HDT/AuNPs electrode was

Sensitive voltammetric determination of vanillin with an AuPd nanoparticles-graphene composite modified electrode.

Science.gov (United States)

Shang, Lei; Zhao, Faqiong; Zeng, Baizhao

2014-05-15

In this work, graphene oxide was reduced to graphene with an endogenous reducing agent from dimethylformamide, and then AuPd alloy nanoparticles were electrodeposited on the graphene film. The obtained AuPd-graphene hybrid film was characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction and voltammetry. The electrochemical behavior of vanillin was studied using the AuPd-graphene hybrid based electrode. It presented high electrocatalytic activity and vanillin could produce a sensitive oxidation peak at it. Under the optimal conditions, the peak current was linear to the concentration of vanillin in the ranges of 0.1-7 and 10-40 μM. The sensitivities were 1.60 and 0.170 mA mM(-1) cm(-2), respectively; the detection limit was 20 nM. The electrode was successfully applied to the detection of vanillin in vanilla bean, vanilla tea and biscuit samples. Copyright © 2013 Elsevier Ltd. All rights reserved.

The Au modified Ge(1 1 0) surface

Science.gov (United States)

Zhang, L.; Kabanov, N. S.; Bampoulis, P.; Saletsky, A. M.; Zandvliet, H. J. W.; Klavsyuk, A. L.

2018-05-01

The pristine Ge(1 1 0) surface is composed of Ge pentagons, which are arranged in relatively large (16 × 2) and c(8 × 10) unit cells. The deposition of sub-monolayer amounts of Au and mild annealing results into de-reconstructed Ge(1 1 0) regions completely free of Ge pentagons and regions composed of nanowires that are aligned along the high symmetry [ 1 1 bar 0 ] direction of the Ge(1 1 0) surface. The de-reconstructed Ge(1 1 0) regions consist of atomic rows that are aligned along the [ 1 1 bar 0 ] direction. A substantial fraction of these substrate rows are straight and resemble the atom rows of the unreconstructed, i.e. bulk terminated, Ge(1 1 0) surface, whereas the other substrate rows have a meandering appearance. These meandering atom rows are comprised of two types of atoms, one type that appears dim, whereas the other type appears bright in filled-state scanning tunneling microscopy images. Using density functional theory calculations, we have tested more than 20 different atomic models for the meandering atom rows. The density functional theory calculations reveal that it is energetically favorable for the deposited Au atoms to exchange position with Ge atoms in the first layer. Based on these findings we conclude that the bright atoms are Ge atoms, whereas the dim atoms are Au atoms.

Tunneling anisotropic magnetoresistance in Co/AIOx/Al tunnel junctions with fcc Co (111) electrodes

NARCIS (Netherlands)

Wang, Kai; Tran, T. Lan Ahn; Brinks, Peter; Brinks, P.; Sanderink, Johannes G.M.; Bolhuis, Thijs; van der Wiel, Wilfred Gerard; de Jong, Machiel Pieter

2013-01-01

Tunneling anisotropic magnetoresistance (TAMR) has been characterized in junctions comprised of face-centered cubic (fcc) Co (111) ferromagnetic electrodes grown epitaxially on sapphire substrates, amorphous AlOx tunnel barriers, and nonmagnetic Al counterelectrodes. Large TAMR ratios have been

Ultraflat Au nanoplates as a new building block for molecular electronics.

Science.gov (United States)

Jeong, Wooseok; Lee, Miyeon; Lee, Hyunsoo; Lee, Hyoban; Kim, Bongsoo; Park, Jeong Young

2016-05-27

We demonstrate the charge transport properties of a self-assembled organic monolayer on Au nanoplates with conductive probe atomic force microscopy (CP-AFM). Atomically flat Au nanoplates, a few hundred micrometers on each side, that have only (111) surfaces, were synthesized using the chemical vapor transport method; these nanoplates were employed as the substrates for hexadecanethiol (HDT) self-assembled monolayers (SAMs). Atomic-scale high-resolution images show (√3 x √3) R30° molecular periodicity, indicating a well-ordered structure of the HDT on the Au nanoplates. We observed reduced friction and adhesion forces on the HDT SAMs on Au nanoplates, compared with Si substrates, which is consistent with the lubricating nature of HDT SAMs. The electrical properties, such as I-V characteristics and current as a function of load, were measured using CP-AFM. We obtained a tunneling decay constant (β) of 0.57 Å(-1), including through-bond (βtb = 0.99 Å(-1)) and through-space (βts = 1.36 Å(-1)) decay constants for the two-pathway model. This indicates that the charge transport properties of HDT SAMs on Au nanoplates are consistent with those on a Au (111) film, suggesting that SAMs on nanoplates can provide a new building block for molecular electronics.

Hydrodeoxygenation of Phenol to Benzene and Cyclohexane on Rh(111) and Rh(211) Surfaces: Insights from Density Functional Theory

DEFF Research Database (Denmark)

Garcia-Pintos, Delfina; Voss, Johannes; Jensen, Anker Degn

2016-01-01

Herein we describe the C-O cleavage of phenol and cyclohexanol over Rh (111) and Rh (211) surfaces using density functional theory calculations. Our analysis is complemented by a microkinetic model of the reactions, which indicates that the C-O bond cleavage of cyclohexanol is easier than that of...

Surface diffusion coefficient of Au atoms on single layer graphene grown on Cu

Energy Technology Data Exchange (ETDEWEB)

Ruffino, F., E-mail: francesco.ruffino@ct.infn.it; Cacciato, G.; Grimaldi, M. G. [Dipartimento di Fisica ed Astronomia-Universitá di Catania, via S. Sofia 64, 95123 Catania, Italy and MATIS IMM-CNR, via S. Sofia 64, 95123 Catania (Italy)

2014-02-28

A 5 nm thick Au film was deposited on single layer graphene sheets grown on Cu. By thermal processes, the dewetting phenomenon of the Au film on the graphene was induced so to form Au nanoparticles. The mean radius, surface-to-surface distance, and surface density evolution of the nanoparticles on the graphene sheets as a function of the annealing temperature were quantified by scanning electron microscopy analyses. These quantitative data were analyzed within the classical mean-field nucleation theory so to obtain the temperature-dependent Au atoms surface diffusion coefficient on graphene: D{sub S}(T)=[(8.2±0.6)×10{sup −8}]exp[−(0.31±0.02(eV)/(at) )/kT] cm{sup 2}/s.

Electrochemical characterization of the underpotential deposition of tellurium on Au electrode

International Nuclear Information System (INIS)

Zhu, W.; Yang, J.Y.; Zhou, D.X.; Bao, S.Q.; Fan, X.A.; Duan, X.K.

2007-01-01

Electrochemical characterization of the underpotential deposition (UPD) of tellurium on Au substrate has been performed in this paper. The mechanism of Te deposition and its voltammetry dependence on the Te ion concentration were studied, and it suggests that variations in the metal ion concentration may affect the UPD process kinetics. The effect of tellurium adsorbates on UPD behavior of Te has also been investigated. The results show that the tellurium adsorbates could be irreversibly adsorbed upon the Au substrate surface under the open-circuit conditions. Subsequent removal of the Te adsorbates was also proved to be very difficult within the Au double-layer region, and a standard electrochemical cleaning procedure is necessary to remove the Te adsorbates completely. When the potential was cycled into the Au oxidation region, a substantial loss of Te adsobates was observed, which occurs simultaneously with the Au oxidation features. Scan rate dependent cyclic voltammetry experiments reveal that the peak current in the Te UPD peak is not a linear function of the scan rate, ν, but of a 2/3 power of the scan rate, ν 2/3 . It is in good consistent with a two-dimension nucleation and growth mechanism

Selective electronalysis of peracetic acid in the presence of a large excess of H2O2 at Au(1 1 1)-like gold electrode

International Nuclear Information System (INIS)

Awad, M.I.

2012-01-01

Highlights: ► Analysis of peracetic acid in the presence of a large excess of H 2 O 2 is introduced. ► Au(1 1 1)-like gold electrode serves as an ideal for this purpose. ► The analysis is characterized by high selectivity and sensitivity. - Abstract: 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 (1 1 1)-like gold electrode in acetate buffer solutions of pH 5.4. Au(1 1 1)-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(1 1 1) facets of the poly-Au electrode, keeping the other two facets (i.e., Au(1 1 0) and Au(1 0 0)) under the protection of the adsorbed cysteine. It has been found that Au(1 1 1)-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.

Above-surface neutralization of multicharged ions incident on a cesiated Au target

International Nuclear Information System (INIS)

Meyer, F.W.; Hughes, I.G.; Overbury, S.H.

1992-01-01

The critical distance above the surface at which conduction band electrons can start to neutralize incident multicharged projectiles by classical overbarrier transitions is inversely proportional to the metal work function. By varying the amount of Cs coverage on a Au single crystal target between O and 1 monolayers, the authors have been able to verify an up to 3.3 eV decrease of the surface work function, corresponding to more than a factor of two decrease relative to that tabulated for clean Au. This change should result in more than doubling the above-surface interaction time. At larger above-surface distances, however, the electron capture most likely occurs into higher principal quantum numbers of the projectile. The subsequent de-excitation cascade by which inner shells of the projectiles are populated may thus require more time. The authors have investigated the overall effect that lowering the work function has on the above-surface component of projectile K-Auger electron emission for grazing incidence N 6+ ions interacting with cesiated Au single crystals. They will present results showing that an enhancement of this component is indeed observed, and that it is strongly dependent on incidence angle

Binary molecular layers of C-60 and copper phthalocyanine on Au(111) : Self-organized nanostructuring

NARCIS (Netherlands)

Stöhr, Meike; Wagner, Thorsten; Gabriel, Markus; Weyers, Bastian; Möller, Rolf

The binary molecular system of C-60 and copper phthalocyanine(CuPc) molecules has been investigated by scanning tunneling microscopy (STM) at room temperature and at 50 K. As substrate Au(111) was chosen. When C-60 and CuPc molecules are sequentially deposited, it is found that well-ordered domains

Electrochemical Oxidation of Glycerol Using Gold Electrode

International Nuclear Information System (INIS)

Mohamed Rozali Othman; Amirah Ahmad

2015-01-01

Cyclic voltammetry, potential linear V and chronocuolometry methods were carried out to gain electrochemical behavior of glycerol at a gold electrode. Potassium hydroxide and sulfuric acid were chosen to be the electrolyte for the electro-oxidation of this organic compound. Besides gold plate electrode, gold composite electrode (Au-PVC) was also used as the working electrode. The Au-PVC composite electrode was characterized by Scanning Electron Microscopy (SEM) to determine its morphological aspects before and after used in electrochemical oxidation of glycerol. In alkaline solution, the adsorption of hydroxide species onto the surface of both gold plate and composite Au-PVC electrodes occurs at potential around 500 mV vs SCE. However, at gold plate electrode, there was a small, broad peak before the drastic escalation of current densities which indicates the charge transfer of the chemisorbed OH - anion. In acidic media, the gold oxide was formed after potential 1.0 V. From the cyclic voltammogram glycerol undergo oxidation twice in potassium hydroxide at gold plate and Au-PVC composite electrodes, while in sulfuric acid, oxidation reaction happened once for glycerol on the gold plate electrode. Overall, electrochemical oxidation of glycerol was more effective in alkaline media. Tafel graph which plotted from potential linear V method shows that Au-PVC composite electrode is better than gold plate electrode for the electro-oxidation of glycerol in alkaline solution. Electrochemical oxidation of glycerol products as analyzed by Gas Chromatography-Mass Spectrometry (GC-MS) produced several carboxylic acids and phenolic compounds. (author)

Surface-enhanced Raman scattering from silver electrodes

International Nuclear Information System (INIS)

Trott, G.R.

1982-01-01

The chemical and physical origins of the anomalously large enhancement of the Raman scattering cross section for molecules adsorbed on silver electrodes in an electrochemical cell were investigated. The effect of the chemical reactions which occur during the anodization/activation procedure were studied using the Ag-CN system. It was shown that the function of the anodization process is to roughen the electrode surface and create an activated site for bonding to the cyanide. A new nonelectrochemical technique for activating the silver surface, along with a study of the enhanced cyanide Raman scattering in different background electrolytes, showed that the Raman active entity on the surface must be a silver-cyanide complex. In order to study the physical mechanism of the enhancement, the angular dependence of the scattered radiation was measured from pyridine adsorbed on an evaporated silver electrode. Both polycrystalline and single crystalline silver films were used. The angular dependence of the scattered radiation from these films showed that the metal surface was controlling the directional properties of the scattered radiation, and not the polarizability tensor of the adsorbate. Based on these experimental results, it was concluded that for weakly roughened silver electrodes the source of the anomalous enhancement is due to a resonant Raman scattering process

Gold work function reduction by 2.2 eV with an air-stable molecular donor layer

Energy Technology Data Exchange (ETDEWEB)

Broeker, Benjamin; Blum, Ralf-Peter; Frisch, Johannes; Rabe, Juergen P.; Koch, Norbert [Institut fuer Physik, Humboldt-Universitaet zu Berlin (Germany); Vollmer, Antje [Berliner Elektronenspeicherring-Gesellschaft fuer Synchrotronstrahlung mbH, Berlin (Germany); Hofmann, Oliver T.; Zojer, Egbert [Institut of Solid State Physics, Graz University of Technology (Austria); Rieger, Ralph; Muellen, Klaus [Max Planck Institut fuer Polymerforschung, Mainz (Germany)

2009-07-01

Ultraviolet photoelectron spectroscopy was used to investigate neutral methyl viologen (1,1'-dimethyl-1H,1'H-[4,4']bipyridinylidene, MV0) deposited on Au(111) surfaces. As a result of molecule-to-metal electron transfer, the work function of Au(111) was decreased from 5.5 eV to 3.3 eV. The energy levels of electron transport layers deposited on top of modified Au surfaces were shifted to higher binding energy compared to layers on pristine Au, and the electron injection barrier was reduced by 0.8 eV for tris(8-hydroxyquinoline)aluminum (Alq3) and by 0.7 eV for C60. The air-stable donor MV0 can thus be used to facilitate electron injection into organic semiconductors even from high work function metals.

Modification of Au surfaces using new ferrocene derivatives

International Nuclear Information System (INIS)

Diaz-Ortiz, Tanya L.; Malave-Leon, Maria; Rivera-Claudio, Mirna; Castillo-Ramirez, Jorge; Cabrera-Martinez, Carlos R.; Brito-Gomez, Rosa; Tremont, Rolando J.

2008-01-01

Gold surfaces have been modified by self-assembled techniques. Here the adsorption time of diasteroisomers (1R, 3S)-1-ferrocenyl-3-methyl-4,4-diphenyl-2,5-dioxacyclopentane and (1S, 3S)-1-ferrocenyl-3-methyl-4,4-diphenyl-2,5-dioxacyclopentane (, 3a and 3b) at a Au surface in ethanol solution was controlled. This study was followed by electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS) analysis. The method used for the surface modification was the control of exposure time of a Au surface in the modifier/ethanol solution. It was demonstrated by EIS and XPS that the Au surface was modified with mixture of compounds 3a + 3b, avoiding the electron transference in the interface. It was also observed that the organometallic molecule indeed had been adsorbed on the Au surface. In addition, evidence seems to conclude that the molecule-Au interaction is through the electrons of cyclopentadienyl moiety, where the oxygen atoms are near the air-molecule interface and the iron atom is near the Au surface. This type of interaction of the ferrocene derivatives with gold surfaces has not been reported by any other author

Alkyl-terminated Si(111) surfaces: A high-resolution, core level photoelectron spectroscopy study

Energy Technology Data Exchange (ETDEWEB)

Terry, J.; Linford, M.R.; Wigren, C.; Cao, R.; Pianetta, P.; Chidsey, C.E. [Stanford University, Stanford, California 94309 (United States)

1999-01-01

The bonding of alkyl monolayers to Si(111) surfaces has been studied with high-resolution core level photoelectron spectroscopy (PES). Two very different wet-chemical methods have been used to prepare the alkyl monolayers: (i) Olefin insertion into the H{endash}Si bond of the H{endash}Si(111) surface, and (ii) replacement of Cl on the Cl{endash}Si(111) surface by an alkyl group from an alkyllithium reagent. In both cases, PES has revealed a C 1s component shifted to lower binding energy and a Si 2p component shifted to higher binding energy. Both components are attributed to the presence of a C{endash}Si bond at the interface. Along with photoelectron diffraction data [Appl. Phys. Lett. {bold 71}, 1056, (1997)], these data are used to show that these two synthetic methods can be used to functionalize the Si(111) surface. {copyright} {ital 1999 American Institute of Physics.}

The photovoltaic performance of Ag2S quantum dots-sensitized solar cells using plasmonic Au nanoparticles/TiO2 working electrodes

Science.gov (United States)

Badawi, Ali; Mostafa, Nasser Y.; Al-Hosiny, Najm M.; Merazga, Amar; Albaradi, Ateyyah M.; Abdel-Wahab, F.; Atta, A. A.

2018-06-01

The photovoltaic performance of silver sulfide (Ag2S) quantum dots-sensitized solar cells (QDSSCs) using different concentrations (0, 0.05, 0.1, 0.3 and 0.5 wt.%) of plasmonic Au nanoparticles (NPs)/titania (TiO2) electrodes has been investigated. Ag2S quantum dots (QDs) were adsorbed onto the Au NPs/titania electrodes using the successive ionic layer adsorption and reaction (SILAR) deposition technique. The morphological properties of the Au NPs and the prepared titania electrodes were characterized using transmission electron microscope (TEM) and scanning electron microscope (SEM), respectively. The energy-dispersive X-ray (EDX) spectra of the bare titania and Ag2S QDs-sensitized titania electrodes were recorded. The optical properties of the prepared Ag2S QDs-sensitized titania electrodes were measured using a UV-visible spectrophotometer. The estimated energy band gap of Ag2S QDs-sensitized titania electrodes is 1.96 eV. The photovoltaic performance of the assembled Ag2S QDSSCs was measured under 100 mW/cm2 solar illumination. The optimal photovoltaic parameters were obtained as follows: open circuit voltage Voc = 0.50 V, current density Jsc = 3.18 mA/cm2, fill factor (FF) = 0.35 and energy conversion efficiency η = 0.55% for 0.3 wt.% of Au NPs/titania electrode. These results are attributed to the enhancement in the absorption and decrease in the electron-hole pairs recombination rate. The open circuit voltage decay (OCVD) measurements of the assembled Ag2S QDSSCs were measured. The calculated electron lifetime (τ) in Ag2S QDSSCs with Au NPs/titania electrodes is at least one order of magnitude more than that with bare titania electrode. The cut-on-cut-off cycles of the solar illumination measurements show the rapid sensitivity and good reproducibility of the assembled Ag2S QDSSCs.

Surface Chemistry Involved in Epitaxy of Graphene on 3C-SiC(111/Si(111

Directory of Open Access Journals (Sweden)

Abe Shunsuke

2010-01-01

Full Text Available Abstract Surface chemistry involved in the epitaxy of graphene by sublimating Si atoms from the surface of epitaxial 3C-SiC(111 thin films on Si(111 has been studied. The change in the surface composition during graphene epitaxy is monitored by in situ temperature-programmed desorption spectroscopy using deuterium as a probe (D2-TPD and complementarily by ex situ Raman and C1s core-level spectroscopies. The surface of the 3C-SiC(111/Si(111 is Si-terminated before the graphitization, and it becomes C-terminated via the formation of C-rich (6√3 × 6√3R30° reconstruction as the graphitization proceeds, in a similar manner as the epitaxy of graphene on Si-terminated 6H-SiC(0001 proceeds.

Electrocatalytic oxidation of cellulose at a gold electrode.

Science.gov (United States)

Sugano, Yasuhito; Latonen, Rose-Marie; Akieh-Pirkanniemi, Marceline; Bobacka, Johan; Ivaska, Ari

2014-08-01

The electrochemical properties of cellulose dissolved in NaOH solution at a Au surface were investigated by cyclic voltammetry, FTIR spectroscopy, the electrochemical quartz crystal microbalance technique, and electrochemical impedance spectroscopy. The reaction products were characterized by SEM, TEM, and FTIR and NMR spectroscopy. The results imply that cellulose is irreversibly oxidized. Adsorption and desorption of hydroxide ions at the Au surface during potential cycling have an important catalytic role in the reaction (e.g., approach of cellulose to the electrode surface, electron transfer, adsorption/desorption of the reaction species at the electrode surface). Moreover, two types of cellulose derivatives were obtained as products. One is a water-soluble cellulose derivative in which some hydroxyl groups are oxidized to carboxylic groups. The other derivative is a water-insoluble hybrid material composed of cellulose and Au nanoparticles (≈4 nm). Furthermore, a reaction scheme of the electrocatalytic oxidation of cellulose at a gold electrode in a basic medium is proposed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Silicon and Germanium (111) Surface Reconstruction

Science.gov (United States)

Hao, You Gong

Silicon (111) surface (7 x 7) reconstruction has been a long standing puzzle. For the last twenty years, various models were put forward to explain this reconstruction, but so far the problem still remains unsolved. Recent ion scattering and channeling (ISC), scanning tunneling microscopy (STM) and transmission electron diffraction (TED) experiments reveal some new results about the surface which greatly help investigators to establish better models. This work proposes a silicon (111) surface reconstruction mechanism, the raising and lowering mechanism which leads to benzene -like ring and flower (raised atom) building units. Based on these building units a (7 x 7) model is proposed, which is capable of explaining the STM and ISC experiment and several others. Furthermore the building units of the model can be used naturally to account for the germanium (111) surface c(2 x 8) reconstruction and other observed structures including (2 x 2), (5 x 5) and (7 x 7) for germanium as well as the (/3 x /3)R30 and (/19 x /19)R23.5 impurity induced structures for silicon, and the higher temperature disordered (1 x 1) structure for silicon. The model is closely related to the silicon (111) surface (2 x 1) reconstruction pi-bonded chain model, which is the most successful model for the reconstruction now. This provides an explanation for the rather low conversion temperature (560K) of the (2 x 1) to the (7 x 7). The model seems to meet some problems in the explanation of the TED result, which is explained very well by the dimer, adatom and stacking fault (DAS) model proposed by Takayanagi. In order to explain the TED result, a variation of the atomic scattering factor is proposed. Comparing the benzene-like ring model with the DAS model, the former needs more work to explain the TED result and the later has to find a way to explain the silicon (111) surface (1 x 1) disorder experiment.

(Tl, Sb) and (Tl, Bi) binary surface reconstructions on Ge(111) substrate

Science.gov (United States)

Gruznev, D. V.; Bondarenko, L. V.; Tupchaya, A. Y.; Yakovlev, A. A.; Mihalyuk, A. N.; Zotov, A. V.; Saranin, A. A.

2018-03-01

2D compounds made of Group-III and Group-V elements on the surface of silicon and germanium attract considerable attention due to prospects of creating III-V binary monolayers, which are predicted to hold advanced physical properties. In the present work, we have investigated two such systems, (Tl, Sb)/Ge(111) and (Tl, Bi)/Ge(111) using scanning tunneling microscopy, low energy electron diffraction observations and density-functional-theory calculations. In addition to the previously reported surface structures of 2D (Tl, Sb) and (Tl, Bi) compounds on Si(111), we found new ones, namely, √{ 7} × √{ 7} and 3 × 3. Formation processes and plausible models of their atomic arrangements are discussed.

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

International Nuclear Information System (INIS)

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

2014-01-01

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 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

Correlação entre a estrutura atômica superficial e o processo de adsorção-dessorção reversível de hidrogênio em eletrodos monocristalinos Pt(111, Pt(100 e Pt(110 The correlation between the atomic surface structure and the reversible adsorption-desorption of hydrogen on single crystal Pt (111, Pt (100 and Pt (110 electrodes

Directory of Open Access Journals (Sweden)

Valderi Pacheco dos Santos

2001-12-01

Full Text Available Platinum is widely used as electrode in electrocatalytic processes, however the use of polycrystalline electrodes introduces a series of variables in the electrochemical system due to the aleatory contribution of all the crystallographic orientations with different surface packing of atoms. Single crystal platinum electrodes of low Miller index present surface structure of high regularity and serve as model to establish a correlation among the macroscopic and microscopic properties of the electrochemical interface. Therefore, the main aim of this work is the study of the voltammetric profiles of the reversible adsorption-desorption of hydrogen on Pt(100, Pt(110 and Pt(111, in order to correlate the electrochemical properties of each different orientation with the surface atomic structure.

High index surfaces of Au-nanocrystals supported on one-dimensional MoO3-nanorod as a bi-functional electrocatalyst for ethanol oxidation and oxygen reduction

International Nuclear Information System (INIS)

Karuppasamy, L.; Chen, C.Y.; Anandan, S.; Wu, J.J.

2017-01-01

Highlights: •Synthesis of a new class of Au nanocrystals enclosed with high index surface supported on MoO 3 nanorods by ultrasonic probe method. •The role of supporting materials reduces the loading of Au and acts as a co-catalyst. •The as prepared electrocatalyst exhibits enhanced catalytic activity and stability towards both EOR and ORR. -- Abstract: The design of highly active electrocatalyst for ethanol electrooxidation (EOR) and oxygen reduction reaction (ORR) is of great significance for the improvement of efficient direct ethanol fuel cells (DEFCs). Therefore, creating high index facets nanocrystals with abundant catalytic active sites of stepped atoms is an effective way to enhance the electrocatalytic performance. In this article, we prepared the high index surface structures of Au nanocrystals supported on one-dimensional (1-D) MoO 3 nanorods by using two steps ultrasonic probe irradiation method. The size and physical properties of as electrocatalysts were studied by using field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), and x-ray diffraction (XRD) instrumentation. Besides, the catalytic activity of as Au-MoO 3 electrocatalyst was determined by using cyclic voltammetry (CV), chronoamperometric (CA), electrochemical impedance spectroscopy (EIS), CO-stripping, and linear sweep voltammetry-rotating disk electrode (LSV-RDE). As a consequence, the Au-MoO 3 nanocomposites has been considered as an effective electrocatalyst for both ethanol oxidation and oxygen reduction reaction.

Switching and sensing spin states of co-porphyrin in bimolecular reactions on Au111 using scanning tunneling microscopy.

Science.gov (United States)

Kim, Howon; Chang, Yun Hee; Lee, Soon-Hyeong; Kim, Yong-Hyun; Kahng, Se-Jong

2013-10-22

Controlling and sensing spin states of magnetic molecules at the single-molecule level is essential for spintronic molecular device applications. Here, we demonstrate that spin states of Co-porphyrin on Au(111) can be reversibly switched over by binding and unbinding of the NO molecule and can be sensed using scanning tunneling microscopy and spectroscopy (STM and STS). Before NO exposure, Co-porphryin showed a clear zero-bias peak, a signature of Kondo effect in STS, whereas after NO exposures, it formed a molecular complex, NO-Co-porphyrin, that did not show any zero-bias feature, implying that the Kondo effect was switched off by binding of NO. The Kondo effect could be switched back on by unbinding of NO through single-molecule manipulation or thermal desorption. Our density functional theory calculation results explain the observations with pairing of unpaired spins in dz(2) and ppπ* orbitals of Co-porphyrin and NO, respectively. Our study opens up ways to control molecular spin state and Kondo effect by means of enormous variety of bimolecular binding and unbinding reactions on metallic surfaces.

Systems and methods for producing low work function electrodes

Science.gov (United States)

Kippelen, Bernard; Fuentes-Hernandez, Canek; Zhou, Yinhua; Kahn, Antoine; Meyer, Jens; Shim, Jae Won; Marder, Seth R.

2015-07-07

According to an exemplary embodiment of the invention, systems and methods are provided for producing low work function electrodes. According to an exemplary embodiment, a method is provided for reducing a work function of an electrode. The method includes applying, to at least a portion of the electrode, a solution comprising a Lewis basic oligomer or polymer; and based at least in part on applying the solution, forming an ultra-thin layer on a surface of the electrode, wherein the ultra-thin layer reduces the work function associated with the electrode by greater than 0.5 eV. According to another exemplary embodiment of the invention, a device is provided. The device includes a semiconductor; at least one electrode disposed adjacent to the semiconductor and configured to transport electrons in or out of the semiconductor.

Catalytically favorable surface patterns in Pt-Au nanoclusters

KAUST Repository

Mokkath, Junais Habeeb

2013-01-01

Motivated by recent experimental demonstrations of novel PtAu nanoparticles with highly enhanced catalytic properties, we present a systematic theoretical study that explores principal catalytic indicators as a function of the particle size and composition. We find that Pt electronic states in the vicinity of the Fermi level combined with a modified electron distribution in the nanoparticle due to Pt-to-Au charge transfer are the origin of the outstanding catalytic properties. From our model we deduce the catalytically favorable surface patterns that induce ensemble and ligand effects. © The Royal Society of Chemistry 2013.

Potentiodynamic formation of gold nanoparticles film on glassy carbon electrode using aminophenyl diazonium cations grafted gold nanoparticles: Determination of histamine H2 receptor antagonist

International Nuclear Information System (INIS)

Kesavan, Srinivasan; Revin, S. Brillians; John, S. Abraham

2014-01-01

Graphical abstract: - Highlights: • Grafting based AuNPs were synthesized in aqueous medium by spontaneous grafting. • GC/ITO electrode was modified with AuNPs film by potentiodynamic method. • AuNPs film modified electrode was characterized by XPS, AFM and CV. • Simultaneous determination of ranitidine and paracetamol was demonstrated. • Practical application was demonstrated in commercial drugs. - Abstract: The aminophenyl (AP) functionalized AuNPs (AP-AuNPs) were synthesized in aqueous medium by spontaneous grafting method and were used for the formation of AuNPs film on glassy carbon (GC) and indium tin oxide (ITO) surfaces by potentiodynamic method. The formed AP-AuNPs film modified electrodes were characterized by cyclic voltammetry (CV), atomic force microscopy (AFM), electrochemical impedance spectroscopy (EIS), and X-ray photoelectron spectroscopy (XPS). EIS studies show that the electron transfer reaction of [Fe(CN) 6 ] 3-/4− was higher at the AP-AuNPs film modified electrode (1.58 × 10 −4 cm s −1 ) than at bare (3.78 × 10 −5 cm s −1 ) GC electrode. The surface coverage of the AP-AuNPs film modified electrode was found to be 4.4 × 10 −10 mol cm −2 . The film formation takes place via -NH 2 groups of AP-AuNPs, which was confirmed by XPS from the observed peaks corresponding to =N-H (396.7 eV), -N-H (399.2 eV), -N = N- (400.2 eV) and -N + -H (403.3 eV). The AP-AuNPs film modified electrode was successfully utilized for the determination of histamine H 2 receptor antagonist ranitidine (RA). Further, the AP-AuNPs film modified electrode was effectively used for the selective determination of RA in the presence of 40-fold excess paracetamol. The present method was successfully used to determine the concentration of RA in commercial drugs

Sudden Intensity Increases and Radial Gradient Changes of Cosmic Ray Mev Electrons and Protons Observed at Voyager 1 Beyond 111 AU in the Heliosheath

Science.gov (United States)

Webber, W. R.; Mcdonald, F. B.; Cummings, A. C.; Stone, E. C.; Heikkila, B.; Lal, N.

2012-01-01

Voyager 1 has entered regions of different propagation conditions for energetic cosmic rays in the outer heliosheathat a distance of about 111 AU from the Sun. The low energy 614 MeV galactic electron intensity increased by 20over a time period 10 days and the electron radial intensity gradient abruptly decreased from 19AU to 8AU at2009.7 at a radial distance of 111.2 AU. At about 2011.2 at a distance of 116.6 AU a second abrupt intensity increase of25 was observed for electrons. After the second sudden electron increase the radial intensity gradient increased to18AU. This large positive gradient and the 13 day periodic variations of 200 MeV particles observed near theend of 2011 indicate that V1 is still within the overall heliospheric modulating region. The implications of these resultsregarding the proximity of the heliopause are discussed.

The role of charge transfer in the oxidation state change of Ce atoms in the TM13-CeO2(111) systems (TM = Pd, Ag, Pt, Au): a DFT + U investigation.

Science.gov (United States)

Tereshchuk, Polina; Freire, Rafael L H; Ungureanu, Crina G; Seminovski, Yohanna; Kiejna, Adam; Da Silva, Juarez L F

2015-05-28

Despite extensive studies of transition metal (TM) clusters supported on ceria (CeO2), fundamental issues such as the role of the TM atoms in the change in the oxidation state of Ce atoms are still not well understood. In this work, we report a theoretical investigation based on static and ab initio molecular dynamics density functional theory calculations of the interaction of 13-atom TM clusters (TM = Pd, Ag, Pt, Au) with the unreduced CeO2(111) surface represented by a large surface unit cell and employing Hubbard corrections for the strong on-site Coulomb correlation in the Ce f-electrons. We found that the TM13 clusters form pyramidal-like structures on CeO2(111) in the lowest energy configurations with the following stacking sequence, TM/TM4/TM8/CeO2(111), while TM13 adopts two-dimensional structures at high energy structures. TM13 induces a change in the oxidation state of few Ce atoms (3 of 16) located in the topmost Ce layer from Ce(IV) (itinerant Ce f-states) to Ce(III) (localized Ce f-states). There is a charge flow from the TM atoms to the CeO2(111) surface, which can be explained by the electronegativity difference between the TM (Pd, Ag, Pt, Au) and O atoms, however, the charge is not uniformly distributed on the topmost O layer due to the pressure induced by the TM13 clusters on the underlying O ions, which yields a decrease in the ionic charge of the O ions located below the cluster and an increase in the remaining O ions. Due to the charge flow mainly from the TM8-layer to the topmost O-layer, the charge cannot flow from the Ce(IV) atoms to the O atoms with the same magnitude as in the clean CeO2(111) surface. Consequently, the effective cationic charge decreases mainly for the Ce atoms that have a bond with the O atoms not located below the cluster, and hence, those Ce atoms change their oxidation state from IV to III. This increases the size of the Ce(III) compared with the Ce(IV) cations, which builds-in a strain within the topmost Ce layer, and

Surface Relaxation and Electronic States of Pt(111) Surface with Varying Slab Thickness

International Nuclear Information System (INIS)

Kaushal, Ashok K.; Mullick, Shanta; Ahluwalia, P. K.

2011-01-01

Surface relaxation and electronic DOS's of Pt(111) surface have been studied with varying slab thickness using ab-initio SIESTA method. We found the expansion in the top layer and contraction in the subsurface layers of Pt(111) surface. Our results match with the experimental results. Also observing electronic density of states we found that as we increase the thickness of slab, the PDOS of Pt(111) surface goes towards the bulk density of states and Fermi energy shifts towards the bulk fermi energy.

Water dissociation on Ni(100) and Ni(111): Effect of surface temperature on reactivity

International Nuclear Information System (INIS)

Seenivasan, H.; Tiwari, Ashwani K.

2013-01-01

Water adsorption and dissociation on Ni(100) and Ni(111) surfaces are studied using density functional theory calculations. Water adsorbs on top site on both the surfaces, while H and OH adsorb on four fold hollow and three fold hollow (fcc) sites on Ni(100) and Ni(111), respectively. Transition states (TS) on both surfaces are identified using climbing image-nudged elastic band method. It is found that the barrier to dissociation on Ni(100) surface is slightly lower than that on Ni(111) surface. Dissociation on both the surfaces is exothermic, while the exothermicity on Ni(100) is large. To study the effect of lattice motion on the energy barrier, TS calculations are performed for various values of Q (lattice atom coordinate along the surface normal) and the change in the barrier height and position is determined. Calculations show that the energy barrier to reaction decreases with increasing Q and increases with decreasing Q on both the surfaces. Dissociation probability values at different surface temperatures are computed using semi-classical approximation. Results show that the influence of surface temperature on dissociation probability on the Ni(100) is significantly larger compared to that of Ni(111). Moreover, on Ni(100), a dramatic shift in energy barrier to lower incident energy values is observed with increasing surface temperature, while the shift is smaller in the case of Ni(111)

An effect of the electrode material on space charge relaxation in ferroelectric copolymers of vinylidene fluoride

Energy Technology Data Exchange (ETDEWEB)

Kochervinskii, Valentin, E-mail: kochval@mail.ru; Pavlov, Alexey; Pakuro, Natalia; Bessonova, Natalia; Shmakova, Nina [State Research Center of the Russian Federation Karpov Institute of Physical Chemistry, Vorontsovo Pole 10, Moscow 103064 (Russian Federation); Malyshkina, Inna [M.V. Lomonosov Moscow State University, Faculty of Physics, Leninskie Gory, Moscow 119991 (Russian Federation); Bedin, Sergey [Moscow State Pedagogical University, 1/1 M. Pirogovskaya Str., Moscow 119991 (Russian Federation); Chubunova, Elena; Lebedinskii, Yuri [National Research Nuclear University MEPhI (Moscow Engineering Physics Institute), Kashirskoe Highway, 31, Moscow 115409 (Russian Federation)

2015-12-28

Processes of relaxation of space charges formed by impurities carriers in isotropic films of vinylidene fluoride and tetrafluoroethylene copolymers of the composition 71/29 and 94/6 were studied. Al and Au symmetric electrodes deposited by evaporation in vacuum have been used. In the case of Al electrodes at temperatures above 100 °C, giant low frequency dielectric dispersion was observed, while it is absent in films with Au electrodes. Causes of this phenomenon were studied by the X-ray photoelectron spectroscopy. It was shown that at Al deposition, new functional groups, such as Al-C, Al-F, and Al{sub 2}O{sub 3}, which are not characteristic of the copolymer film surface, formed. They were supposed to be traps for impurity carriers and because of this the electrode became partially blocked. This led to appearance of the giant electrode polarization on the metal-polymer boundary, which did not take place in the case of Au electrodes. Parameters of the Au4f line for the copolymer with different contents of fluorine atoms in the chain were analyzed. An increase in the number of these atoms was shown to result in the line shift to higher energies. This phenomenon was associated with an increase in the shift of the electron density from Au atoms to the F ones which has a high affinity to electrons.

Determination of work function of graphene under a metal electrode and its role in contact resistance.

Science.gov (United States)

Song, Seung Min; Park, Jong Kyung; Sul, One Jae; Cho, Byung Jin

2012-08-08

Although the work function of graphene under a given metal electrode is critical information for the realization of high-performance graphene-based electronic devices, relatively little relevant research has been carried out to date. In this work, the work function values of graphene under various metals are accurately measured for the first time through a detailed analysis of the capacitance-voltage (C-V) characteristics of a metal-graphene-oxide-semiconductor (MGOS) capacitor structure. In contrast to the high work function of exposed graphene of 4.89-5.16 eV, the work function of graphene under a metal electrode varies depending on the metal species. With a Cr/Au or Ni contact, the work function of graphene is pinned to that of the contacted metal, whereas with a Pd or Au contact the work function assumes a value of ∼4.62 eV regardless of the work function of the contact metal. A study of the gate voltage dependence on the contact resistance shows that the latter case provides lower contact resistance.

Solid-state electrochemiluminescence sensor through the electrodeposition of Ru(bpy)32+/AuNPs/chitosan composite film onto electrode

International Nuclear Information System (INIS)

Yun Wen; Xu Ying; Dong Ping; Ma Xiongxiong; He Pingang; Fang Yuzhi

2009-01-01

Tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy) 3 2+ ) has been successfully immobilized onto electrode through the electrodeposition of Ru(bpy) 3 2+ /AuNPs/chitosan composite film. In the experiments, chitosan solution was first mixed with Au nanoparticles (AuNPs) and Ru(bpy) 3 2+ . Then, during chronopotentiometry experiments in this mixed solution, a porous 3D network structured film containing Ru(bpy) 3 2+ , AuNPs and chitosan has been electrodeposited onto cathode due to the deposition of chitosan when pH value is over its pK a (6.3). The applied current density is crucial to the film thickness and the amount of the entrapped Ru(bpy) 3 2+ . Additionally, these doping Ru(bpy) 3 2+ in the composite film maintained their intrinsic electrochemical and electrochemiluminescence activities. Consequently, this Ru(bpy) 3 2+ /AuNPs/chitosan modified electrode has been used in ECL to detect tripropylamine, and the detection limit was 5 x 10 -10 M

Adsorption of asparagine on the gold electrode and air/solution interface

International Nuclear Information System (INIS)

Slojkowska, R.; Palys, B.; Jurkiewicz-Herbich, M.

2004-01-01

The adsorption of asparagine (Asn) on a gold electrode from 0.1 M LiClO 4 aqueous solutions was investigated. The experimental data obtained from ac impedance measurements were analyzed to determine the dependence of adsorption parameters, i.e. the standard Gibbs energy of adsorption (ΔG 0 ), maximal value of surface excess concentration (Γ max ) of Asn and parameter of interactions in the adsorbed layer (A) on the electrode potential. The relatively large value of Gibbs energy of adsorption (∼ -47 kJ mol -1 ) gives the evidence of a very strong adsorption of Asn at the polycrystalline Au electrode. The comparison of the adsorption behavior of Asn at the air/solution and the Au/solution interfaces points out to the significant electronic interactions of adsorbate molecules with the Au electrode, since the adsorption of Asn on a free surface (from the same solutions) is very week. The analysis of the electrochemical data as well as the infrared reflection absorption spectroscopy (IRAS) results reveal that Asn molecules are anchored to the Au surface through oxygen atoms of the carboxylate group COO - and through the amide carbonyl group

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

Science.gov (United States)

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

2013-09-12

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

Dynamics of Pseudomonas aeruginosa azurin and its Cys3Ser mutant at single crystal gold surfaces investigated by cyclic voltammetry and atomic force microscopy

DEFF Research Database (Denmark)

Friis, Esben P.; Andersen, Jens Enevold Thaulov; Madsen, Lars Lithen

1997-01-01

Cyclic voltammetry of Pseudomonas aeruginosa azurin on polycrystalline gold is reversible (E0=360mV vs she;50mM ammonium acetate) but the voltammetric signals decay with time constants of about 3x10-3 s-1. No signal is observed for monocrystalline Au(111). Cys3Ser azurin is electrochemically inac...... into the solution, recovering the free Au(111) surface. The cyclic voltammetry and AFM data are consistent with time dependent adsorption of the azurins on gold via the disulphide bridge (wild-type) or free thiol group (Cys3Ser mutant).......Cyclic voltammetry of Pseudomonas aeruginosa azurin on polycrystalline gold is reversible (E0=360mV vs she;50mM ammonium acetate) but the voltammetric signals decay with time constants of about 3x10-3 s-1. No signal is observed for monocrystalline Au(111). Cys3Ser azurin is electrochemically...... inactive on either type of gold electrode but shows a reversible although decaying peak (362mV, 50mM ammonium acetate; decay time constant ~ 2x10-3 s-1) on edge-plane pyrolytic graphite.Ex situ and in situ atomic force microscopy (AFM) of the azurins on Au(111) show initially arrays of protein structures...

Adsorption of carbon monoxide on the Si(111)-7 × 7 surface

Energy Technology Data Exchange (ETDEWEB)

Shong, Bonggeun, E-mail: bshong@cnu.ac.kr

2017-05-31

Highlights: • Detailed chemistry of CO with the Si(111)-7 × 7 surface is computationally studied. • On-top on rest-atoms and back-bond insertion on adatoms are suggested geometries. • The two structures exhibit no activation barrier for adsorption and significant stability. • Geometrical and spectroscopic properties of CO adsorbates are predicted. • Direction of the interfacial charge transfer depends on the bonding configuration. - Abstract: The adsorption of CO and surface chemistry of Si are well-understood topics in surface science. However, research into the adsorption of CO on the Si(111)-7 × 7 surface is deficient. In this study, the adsorption of CO on Si(111)-7 × 7 is investigated via high-level density functional theory calculations using cluster model. Two adsorption configurations are found to be kinetically and thermodynamically viable: on-top on rest-atoms and back-bond insertion on adatoms, both binding to the surface via C atom. Structural, electronic, and spectroscopic properties of the adsorbates indicate a σ-donating/π-accepting nature of the CO−Si bonds in both configurations. The domination of σ-donation in the on-top configuration results in a net positive charge on the on-top adsorbate, and the opposite situation yields a net negative charge on the back-bond insertion adsorbates. Our study provides a detailed understanding of the previous experimental observations of fundamental surface chemical phenomena, suggesting possible applications of Si surface functionalization using CO.

In situ observation of a deprotonation driven phase transformation-4,4'-Biphenyldicarboxylic acide on Au(111)

NARCIS (Netherlands)

Schwarz, Daniel; van Gastel, Raoul; Zandvliet, Henricus J.W.; Poelsema, Bene

2013-01-01

We have studied the growth of 4,4′-biphenyldicarboxylic acid (BDA) domains on Au(111) by means of low-energy electron microscopy (LEEM) and selective area low-energy electron diffraction (μLEED). Between 300 and 400 K, BDA forms three different 2-D crystalline phases, which are attributed to

Cyclic voltammograms for H on Pt(111) and Pt(100) from first principles

DEFF Research Database (Denmark)

Karlberg, Gustav; Jaramillo, Thomas; Skulason, Egill

2007-01-01

Cyclic voltammetry is a fundamental experimental method for characterizing electrochemical surfaces. Despite its wide use, a way to quantitatively and directly relate cyclic voltammetry to ab initio calculations has been lacking. We derive the cyclic voltammogram for H on Pt(111) and Pt(100), bas...... solely on density functional theory calculations and standard molecular tables. By relating the gas phase adsorption energy to the electrochemical electrode potential, we provide a direct link between surface science and electrochemistry....

Chemical modifications of Au/SiO2 template substrates for patterned biofunctional surfaces.

Science.gov (United States)

Briand, Elisabeth; Humblot, Vincent; Landoulsi, Jessem; Petronis, Sarunas; Pradier, Claire-Marie; Kasemo, Bengt; Svedhem, Sofia

2011-01-18

The aim of this work was to create patterned surfaces for localized and specific biochemical recognition. For this purpose, we have developed a protocol for orthogonal and material-selective surface modifications of microfabricated patterned surfaces composed of SiO(2) areas (100 μm diameter) surrounded by Au. The SiO(2) spots were chemically modified by a sequence of reactions (silanization using an amine-terminated silane (APTES), followed by amine coupling of a biotin analogue and biospecific recognition) to achieve efficient immobilization of streptavidin in a functional form. The surrounding Au was rendered inert to protein adsorption by modification by HS(CH(2))(10)CONH(CH(2))(2)(OCH(2)CH(2))(7)OH (thiol-OEG). The surface modification protocol was developed by testing separately homogeneous SiO(2) and Au surfaces, to obtain the two following results: (i) SiO(2) surfaces which allowed the grafting of streptavidin, and subsequent immobilization of biotinylated antibodies, and (ii) Au surfaces showing almost no affinity for the same streptavidin and antibody solutions. The surface interactions were monitored by quartz crystal microbalance with dissipation monitoring (QCM-D), and chemical analyses were performed by polarization modulation-reflexion absorption infrared spectroscopy (PM-RAIRS) and X-ray photoelectron spectroscopy (XPS) to assess the validity of the initial orthogonal assembly of APTES and thiol-OEG. Eventually, microscopy imaging of the modified Au/SiO(2) patterned substrates validated the specific binding of streptavidin on the SiO(2)/APTES areas, as well as the subsequent binding of biotinylated anti-rIgG and further detection of fluorescent rIgG on the functionalized SiO(2) areas. These results demonstrate a successful protocol for the preparation of patterned biofunctional surfaces, based on microfabricated Au/SiO(2) templates and supported by careful surface analysis. The strong immobilization of the biomolecules resulting from the described

Ab Initio Calculations of the Electronic Properties of Polypyridine Transition Metal Complexes and Their Adsorption on Metal Surfaces in the Presence of Solvent and Counterions

DEFF Research Database (Denmark)

Jónsson, E. Ö.; Thygesen, Kristian Sommer; Ulstrup, Jens

2011-01-01

Os(II)/(III) and Co(II)/(III) polypyridine complexes in aqueous solution are robust molecular entities both in freely solute state and adsorbed on Au(111)- and Pt(111)-electrode surfaces. This class of robust coordination chemical compounds have recently been characterized by electrochemical...... of the complexes in the presence of the solvent, are conserved upon adsorption, whereas the structural features of the different oxidation states are completely lost upon adsorption under vacuum conditions. Detailed microscopic insight such as offered by the present study will be important in molecular...

One-pot reaction for the preparation of biofunctionalized self-assembled monolayers on gold surfaces

Energy Technology Data Exchange (ETDEWEB)

Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J., E-mail: lwebb@cm.utexas.edu

2017-02-01

Highlights: • One-pot synthesis of α-helical-terminated self-assembled monolayers on Au(111). • Synthesis of high density, structured, and covalently bound α-helices on Au(111). • Characterization by surface-averaged and single molecule techniques. • Peptide-terminated surfaces for fabrication of biomaterials and sensors. - Abstract: The Huisgen cycloaddition reaction (“click” chemistry) has been used extensively to functionalize surfaces with macromolecules in a straightforward manner. We have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to a well-ordered azide-terminated alkanethiol self-assembled monolayer (SAM) on a Au(111) surface. While convenient, click-based strategies potentially pose significant problems from reagents, solvents, and reaction temperatures that may irreversibly damage some molecules or substrates. Tuning click chemistry conditions would allow individual optimization of reaction conditions for a wide variety of biomolecules and substrate materials. Here, we explore the utility of simultaneous SAM formation and peptide-attachment chemistry in a one-pot reaction. We demonstrate that a formerly multistep reaction can be successfully carried out concurrently by mixing azide-terminated alkanethiols, CuCl, and a propargylglycine-containing peptide over a bare gold surface in ethanol and reacting at 70 °C. X-ray photoelectron spectroscopy (XPS), surface infrared spectroscopy, surface circular dichroic (CD) spectroscopy, and scanning tunneling microscopy (STM) were used to determine that this one-pot reaction strategy resulted in a high density of surface-bound α-helices without aggregation. This work demonstrates the simplicity and versatility of a SAM-plus-click chemistry strategy for functionalizing Au surfaces with structured biomolecules.

Textile Electrodes Embedded in Clothing: A Practical Alternative to Traditional Surface Electromyography when Assessing Muscle Excitation during Functional Movements

Directory of Open Access Journals (Sweden)

Steffi L. Colyer, Polly M. McGuigan

2018-03-01

Full Text Available Textile electromyography (EMG electrodes embedded in clothing allow muscle excitation to be recorded in previously inaccessible settings; however, their ability to accurately and reliably measure EMG during dynamic tasks remains largely unexplored. To quantify the validity and reliability of textile electrodes, 16 recreationally active males completed two identical testing sessions, within which three functional movements (run, cycle and squat were performed twice: once wearing EMG shorts (measuring quadriceps, hamstrings and gluteals myoelectric activity and once with surface EMG electrodes attached to the vastus lateralis, biceps femoris and gluteus maximus. EMG signals were identically processed to provide average rectified EMG (normalized to walking and excitation length. Results were compared across measurement systems and demonstrated good agreement between the magnitude of muscle excitation when EMG activity was lower, but agreement was poorer when excitation was higher. The length of excitation bursts was consistently longer when measured using textile vs. surface EMG electrodes. Comparable between-session (day-to-day repeatability was found for average rectified EMG (mean coefficient of variation, CV: 42.6 and 41.2% and excitation length (CV: 12.9 and 9.8% when using textile and surface EMG, respectively. Additionally, similar within-session repeatability (CV was recorded for average rectified EMG (13.8 and 14.1% and excitation length (13.0 and 12.7% for textile and surface electrodes, respectively. Generally, textile EMG electrodes appear to be capable of providing comparable muscle excitation information and reproducibility to surface EMG during dynamic tasks. Textile EMG shorts could therefore be a practical alternative to traditional laboratory-based methods allowing muscle excitation information to be collected in more externally-valid training environments.

Growth and structure of Co/Au magnetic thin films

International Nuclear Information System (INIS)

Marsot, N.

1999-01-01

We have studied the growth and the crystallographic structure of magnetic ultra thin cobalt/gold films (Co/Au), in order to investigate the correlations between their magnetic and structural properties. Room temperature (R.T.) Co growth on Au (111) proceeds in three stages. Up to 2 Co monolayers (ML), a bilayer island growth mode is observed. Between 2 and 5 ML, coalescence of the islands occurs, covering the substrate surface and a Co/Au mixing is observed resulting from the de-construction of the Herringbone reconstruction. Finally, beyond 5 ML, the CoAu mixing is buried and the Co growth continues in a 3-D growth. Annealing studies at 600 K on this system show a smoothing effect of the Co film, and at the same time, segregation of Au atoms. The quality of the Co/Au interface (sharpness) is not enhanced by the annealing. The local order was studied by SEXAFS and the long range order by GIXRD showing that the Co film has a hexagonal close packed structure, with an easy magnetization axis perpendicular to the surface. From a local order point of view, the Co grows with an incoherent epitaxy and keeps its own bulk parameters. The GIXRD analysis shows a residual strain in the Co film of 4%. The difference observed between the local order analysis and the long range order results is explained in terms of the low dimensions of the diffracting domains. The evolution of film strains, as a function of the Co coverage, shows a marked deviation from the elastic strain theory. Modification of the strain field in the Co film as a function of the Au coverage is studied by GIXRD analysis. The Au growth study, at R.T., shows no evidence of a Au/Co mixing in the case of the Au/Co interface. The Au overlayer adopts a twinned face centred cubic structure on the rough Co film surface. (author)

Effect of surface roughness and surface modification of indium tin oxide electrode on its potential response to tryptophan

International Nuclear Information System (INIS)

Khan, Md. Zaved Hossain; Nakanishi, Takuya; Kuroiwa, Shigeki; Hoshi, Yoichi; Osaka, Tetsuya

2011-01-01

Highlights: → We examine factors affecting potential response of ITO electrode to tryptophan. → Surface roughness of ITO electrode affects the stability of its rest potential. → Surface modification is effective for ITO electrode with a certain roughness. → Optimum values of work function exist for potential response of ITO to tryptophan. - Abstract: The effect of surface modification of indium tin oxide (ITO) electrode on its potential response to tryptophan was investigated for ITO substrates with different surface roughness. It was found that a small difference in surface roughness, between ∼1 and ∼2 nm of R a evaluated by atomic force microscopy, affects the rest potential of ITO electrode in the electrolyte. A slight difference in In:Sn ratio at the near surface of the ITO substrates, measured by angle-resolved X-ray photoelectron spectrometry and Auger electron spectroscopy is remarkable, and considered to relate with surface roughness. Interestingly, successive modification of the ITO surface with aminopropylsilane and disuccinimidyl suberate, of which essentiality to the potential response to indole compounds we previously reported, improved the stability of the rest potential and enabled the electrodes to respond to tryptophan in case of specimens with R a values ranging between ∼2 and ∼3 nm but not for those with R a of ∼1 nm. It was suggested that there are optimum values of effective work function of ITO for specific potential response to tryptophan, which can be obtained by the successive modification of ITO surface.

Controlled Synthesis of Au@AgAu Yolk-Shell Cuboctahedra with Well-Defined Facets.

Science.gov (United States)

Londono-Calderon, Alejandra; Bahena, Daniel; Yacaman, Miguel J

2016-08-02

The synthesis of Au@AgAu yolk-shell cuboctahedra nanoparticles formed by galvanic replacement in a seed-mediated method is described. Initially, single-crystal Au seeds are used for the formation of Au@Ag core-shell nanocubes, which serve as the template material for the deposition of an external Au layer. The well-controlled synthesis yields the formation of cuboctahedra nanoparticles with smooth inner and outer Au/Ag surfaces. The deposition/oxidation process is described to understand the formation of cuboctahedra and octahedra nanoparticles. The Au core maintains the initial morphology of the seed and remains static at the center of the yolk-shell because of residual Ag. Structural analysis of the shell indicates intrinsic stacking faults (SFs) near the surface. Energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) compositional analysis show an Au-Ag nonordered alloy forming the shell. The three-dimensional structure of the nanoparticles presented open facets on the [111] as observed by electron tomography SIRT reconstruction over a stack of high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images. The geometrical model was validated by analyzing the direction of streaks in coherent nanobeam diffraction (NBD). The catalytic activity was evaluated using a model reaction based on the reduction of 4-nitrophenol (4-NTP) by NaBH4 in the presence of Au@AgAu yolk-shell nanoparticles.

Carbide induced reconstruction of monatomic steps on Ni(111) - A density functional study

DEFF Research Database (Denmark)

Andersson, Martin; Abild-Pedersen, Frank

2007-01-01

We present density functional calculations for carbon adsorption at the two types of monatomic steps on a Ni(111) surface. We show that it is thermodynamically favourable to make a carbon induced clock-type reconstruction at the close-packed step with a [111] step geometry, which creates fourfold...

Selective electronalysis of peracetic acid in the presence of a large excess of H{sub 2}O{sub 2} at Au(1 1 1)-like gold electrode

Energy Technology Data Exchange (ETDEWEB)

Awad, M.I., E-mail: mawad70@yahoo.com [Department of Chemistry, Faculty of Science, Cairo University (Egypt)

2012-06-12

Highlights: Black-Right-Pointing-Pointer Analysis of peracetic acid in the presence of a large excess of H{sub 2}O{sub 2} is introduced. Black-Right-Pointing-Pointer Au(1 1 1)-like gold electrode serves as an ideal for this purpose. Black-Right-Pointing-Pointer The analysis is characterized by high selectivity and sensitivity. - Abstract: Peracetic acid (PAA) has been selectively electroanalyzed in the presence of a large excess of hydrogen peroxide (H{sub 2}O{sub 2}), about 500 fold that of PAA, using Au (1 1 1)-like gold electrode in acetate buffer solutions of pH 5.4. Au(1 1 1)-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(1 1 1) facets of the poly-Au electrode, keeping the other two facets (i.e., Au(1 1 0) and Au(1 0 0)) under the protection of the adsorbed cysteine. It has been found that Au(1 1 1)-like gold electrode positively shifts the reduction peak of PAA, while, fortunately, shifts the reduction peak of H{sub 2}O{sub 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{sub 2}O{sub 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.

Electrochemical Characterization of O2 Plasma Functionalized Multi-Walled Carbon Nanotube Electrode for Legionella pneumophila DNA Sensor

Science.gov (United States)

Park, Eun Jin; Lee, Jun-Yong; Hyup Kim, Jun; Kug Kim, Sun; Lee, Cheol Jin; Min, Nam Ki

2010-08-01

An electrochemical DNA sensor for Legionella pneumophila detection was constructed using O2 plasma functionalized multi-walled carbon nanotube (MWCNT) film as a working electrode (WE). The cyclic voltammetry (CV) results revealed that the electrocatalytic activity of plasma functionalized MWCNT (pf-MWCNT) significantly changed depending on O2 plasma treatment time due to some oxygen containing functional groups on the pf-MWCNT surface. Scanning electron microscope (SEM) images and X-ray photoelectron spectroscopy (XPS) spectra were also presented the changes of their surface morphologies and oxygen composition before and after plasma treatment. From a comparison study, it was found that the pf-MWCNT WEs had higher electrocatalytic activity and more capability of probe DNA immobilization: therefore, electrochemical signal changes by probe DNA immobilization and hybridization on pf-MWCNT WEs were larger than on Au WEs. The pf-MWCNT based DNA sensor was able to detect a concentration range of 10 pM-100 nM of target DNA to detect L. pneumophila.

Alternating voltage-induced electrochemical synthesis of colloidal Au nanoicosahedra

Energy Technology Data Exchange (ETDEWEB)

McCann, Kevin; Cloud, Jacqueline E.; Yang, Yongan, E-mail: yonyang@mines.edu [Colorado School of Mines, Department of Chemistry and Geochemistry (United States)

2013-11-15

A simple method of alternating voltage-induced electrochemical synthesis has been developed to synthesize highly dispersed colloidal Au nanoicosahedra of 14 ± 3 nm in size. This simple and effective method uses a common transformer to apply a zero-offset alternating voltage to a pair of identical Au electrodes that are immersed in an electrolyte solution containing ligands. The obtained Au nanoicosahedra in this work are among the smallest Au icosahedra synthesized in aqueous solutions. A series of experimental conditions have been studied, such as voltage, the electrolyte identity and concentration, stabilizer identity and concentration, and reaction temperature. The mechanistic study indicates that Au nanoicosahedra are produced on electrode surfaces through an intermediate state of AuO{sub x}. The kinetic rate constant of these Au icosahedra in catalyzing the reduction of 4-nitrophenol with sodium borohydride is found much larger than the literature values of similar Au nanocrystals. In addition, the synthesis of Au–Pd-alloyed NCs has also been attempted.Graphical Abstract.

A micro-structured Si-based electrodes for high capacity electrical double layer capacitors

International Nuclear Information System (INIS)

Krikscikas, Valdas; Oguchi, Hiroyuki; Hara, Motoaki; Kuwano, Hiroki; Yanazawa, Hiroshi

2014-01-01

We challenged to make basis for Si electrodes of electric double layer capacitors (EDLC) used as a power source of micro-sensor nodes. Mcroelectromechanical systems (MEMS) processes were successfully introduced to fabricate micro-structured Si-based electrodes to obtain high surface area which leads to high capacity of EDLCs. Study of fundamental properties revealed that the microstructured electrodes benefit from good wettability to electrolytes, but suffer from electric resistance. We found that this problem can be solved by metal-coating of the electrode surface. Finally we build an EDLC consisting of Au-coated micro-structured Si electrodes. This EDLC showed capacity of 14.3 mF/cm 2 , which is about 530 times larger than that of an EDLC consisting of flat Au electrodes

Surface-modified electrodes (SME)

NARCIS (Netherlands)

Schreurs, J.P.G.M.; Barendrecht, E.

1984-01-01

This review deals with the literature (covered up to August 1983), the characterization and the applications of Surface-Modified Electrodes (SME). As a special class of SME's, the Enzyme-Modified Electrode (EME) is introduced. Three types of modification procedures are distinguished; i.e. covalent

Decomposition mechanism of formic acid on Cu (111) surface: A theoretical study

Energy Technology Data Exchange (ETDEWEB)

Jiang, Zhao, E-mail: jiangzhao@mail.xjtu.edu.cn; Qin, Pei; Fang, Tao

2017-02-28

Highlights: • Adsorption and decomposition mechanism of HCOOH on Cu (111) were investigated using DFT calculations. • The stable co-adsorption configurations of related intermediates were identified. • Five dissociation pathways of HCOOH via initial H−O, C−H and C−O bond scissions were considered and analyzed. - Abstract: The study of formic acid decomposition on transition metal surfaces is important to obtain useful information for vapor phase catalysis involving HCOOH and for the development of direct formic acid fuel cells. In this study, periodic density functional theory calculations have been employed to investigate the dissociation pathways of HCOOH on Cu (111) surface. About adsorption, it is found that the adsorption of HCOO, COOH, HCO, CO, OH and H on Cu (111) are considered chemisorption, whereas HCOOH, CO{sub 2}, H{sub 2}O and H{sub 2} have the weak interaction with Cu (111) surface. Furthermore, the minimum energy pathways are analyzed for the decomposition of HCOOH to CO{sub 2} and CO through the scission of H−O, C−H and C−O bonds. It is found that HCOOH, HCOO and COOH prefer to dissociate in the related reactions rather than desorb. For the decomposition, it is indicated that HCO and COOH are the main dissociated intermediates of trans-HCOOH, CO{sub 2} is the main dissociated intermediates of bidentate-HCOO, and CO is the main dissociated product of cis-COOH. The co-adsorbed H atom is beneficial for the formation of CO{sub 2} from cis-COOH. Besides, it is found that the most favorable path for HCOOH decomposition on Cu (111) surface is HCOOH-HCO-CO (Path 5), where the step of CO formation from HCO dehydrogenation is considered to be the rate-determining step. The results also show that CO is preferentially formed as the dominant product of HCOOH on Cu (111) surface.

Spherical and polygonal shape of Au nanoparticles coated functionalized polymer microspheres

Energy Technology Data Exchange (ETDEWEB)

Xu, Ting; Li, Yingzhi; Zhang, Junxian; Qi, Yalong; Zhao, Xin; Zhang, Qinghua, E-mail: qhzhang@dhu.edu.cn

2015-08-01

Highlights: • PS/PPy with well-defined core/shell structures was prepared in aqueous solution. • Au NPs were coated on PS/PPy by the fixation and continuous growth process. • Mercapto-groups played a role in the number and morphology of Au shell. • PS/PPy/Au had homogeneous and dense Au coatings with different shape. - Abstract: Uniform polystyrene (PS)/polypyrrole (PPy) composite microspheres with well-defined core/shell structures are synthesized by chemical oxidative polymerization. Gold nanoparticles (Au NPs) are successfully coated on the surface of PS/PPy microspheres by means of electrostatic interactions due to the functionalized PPy coatings supplying sufficient amino groups and the additive of mercapto acetic acid. Furthermore, the as-prepared PS/PPy/Au microspheres serving as seeds facilitate Au NPs further growth by in situ reduction in HAuCl{sub 4} solution to obtain PS/PPy/Au spheres with the core/shell/shell structure. Morphology observation demonstrates that the monodisperse PS/PPy/Au microspheres compose of uniform cores and the compact coatings containing distinct two layers. X-ray diffraction and X-ray photoelectron spectroscope confirm the existence of PPy and Au on the surface of the composite spheres. This facile approach to preparing metal-coated polymer spheres supplies the potential applications in biosensors, electronics and medical diagnosis.

A density functional theory study on the carbon chain growth of ethanol formation on Cu-Co (111) and (211) surfaces

Energy Technology Data Exchange (ETDEWEB)

Ren, Bohua; Dong, Xiuqin; Yu, Yingzhe [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin 300072 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Wen, Guobin [Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Zhang, Minhua, E-mail: mhzhang@tju.edu.cn [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin 300072 (China); Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China)

2017-08-01

Highlights: • Calculations based on the first-principle density functional theory were carried out to study ethanol formation from syngas on Cu-Co surfaces. • The most controversial reactions in ethanol formation from syngas were researched: CO dissociation mechanism and the key reactions of carbon chain growth of ethanol formation (HCO insertion reactions (CHx + HCO → CHxCHO (x = 1–3))). • Four model surfaces (Cu-Co (111) and (211) with Cu-rich or Co-rich surfaces) were built to investigate the synergy of the Cu and Co components. • The PDOS of 4d orbitals and d-band center analysis of surface Cu and Co atoms of all surfaces were studied to reveal correlation between electronic property and catalytic performance. - Abstract: Calculations based on the first-principle density functional theory were carried out to study the most controversial reactions in ethanol formation from syngas on Cu-Co surfaces: CO dissociation mechanism and the key reactions of carbon chain growth of ethanol formation (HCO insertion reactions) on four model surfaces (Cu-Co (111) and (211) with Cu-rich or Co-rich surfaces) to investigate the synergy of the Cu and Co components since the complete reaction network of ethanol formation from syngas is a huge computational burden to calculate on four Cu-Co surface models. We investigated adsorption of important species involved in these reactions, activation barrier and reaction energy of H-assisted dissociation mechanism, directly dissociation of CO, and HCO insertion reactions (CH{sub x} + HCO → CH{sub x}CHO (x = 1–3)) on four Cu-Co surface models. It was found that reactions on Cu-rich (111) and (211) surfaces all have lower activation barrier in H-assisted dissociation and HCO insertion reactions, especially CH + HCO → CHCHO reaction. The PDOS of 4d orbitals of surface Cu and Co atoms of all surfaces were studied. Analysis of d-band center of Cu and Co atoms and the activation barrier data suggested the correlation between

A surface-electrode quadrupole guide for electrons

Energy Technology Data Exchange (ETDEWEB)

Hoffrogge, Johannes Philipp

2012-12-19

This thesis reports on the design and first experimental realization of a surface-electrode quadrupole guide for free electrons. The guide is based on a miniaturized, planar electrode layout and is driven at microwave frequencies. It confines electrons in the near-field of the microwave excitation, where strong electric field gradients can be generated without resorting to resonating structures or exceptionally high drive powers. The use of chip-based electrode geometries allows the realization of versatile, microstructured potentials with the perspective of novel quantum experiments with guided electrons. I present the design, construction and operation of an experiment that demonstrates electron confinement in a planar quadrupole guide for the first time. To this end, electrons with kinetic energies from one to ten electron-volts are guided along a curved electrode geometry. The stability of electron guiding as a function of drive parameters and electron energy has been studied. A comparison with numerical particle tracking simulations yields good qualitative agreement and provides a deeper understanding of the electron dynamics in the guiding potential. Furthermore, this thesis gives a detailed description of the design of the surface-electrode layout. This includes the development of an optimized coupling structure to inject electrons into the guide with minimum transverse excitation. I also discuss the extension of the current setup to longitudinal guide dimensions that are comparable to or larger than the wavelength of the drive signal. This is possible with a modified electrode layout featuring elevated signal conductors. Electron guiding in the field of a planar, microfabricated electrode layout allows the generation of versatile and finely structured guiding potentials. One example would be the realization of junctions that split and recombine a guided electron beam. Furthermore, it should be possible to prepare electrons in low-lying quantum mechanical

A surface-electrode quadrupole guide for electrons

International Nuclear Information System (INIS)

Hoffrogge, Johannes Philipp

2012-01-01

This thesis reports on the design and first experimental realization of a surface-electrode quadrupole guide for free electrons. The guide is based on a miniaturized, planar electrode layout and is driven at microwave frequencies. It confines electrons in the near-field of the microwave excitation, where strong electric field gradients can be generated without resorting to resonating structures or exceptionally high drive powers. The use of chip-based electrode geometries allows the realization of versatile, microstructured potentials with the perspective of novel quantum experiments with guided electrons. I present the design, construction and operation of an experiment that demonstrates electron confinement in a planar quadrupole guide for the first time. To this end, electrons with kinetic energies from one to ten electron-volts are guided along a curved electrode geometry. The stability of electron guiding as a function of drive parameters and electron energy has been studied. A comparison with numerical particle tracking simulations yields good qualitative agreement and provides a deeper understanding of the electron dynamics in the guiding potential. Furthermore, this thesis gives a detailed description of the design of the surface-electrode layout. This includes the development of an optimized coupling structure to inject electrons into the guide with minimum transverse excitation. I also discuss the extension of the current setup to longitudinal guide dimensions that are comparable to or larger than the wavelength of the drive signal. This is possible with a modified electrode layout featuring elevated signal conductors. Electron guiding in the field of a planar, microfabricated electrode layout allows the generation of versatile and finely structured guiding potentials. One example would be the realization of junctions that split and recombine a guided electron beam. Furthermore, it should be possible to prepare electrons in low-lying quantum mechanical

The screening effects of the screened exchange hybrid functional in surface systems: A case study on the CO/Pt(111) problem

Energy Technology Data Exchange (ETDEWEB)

Li, H., E-mail: li-huanglong@mail.tsinghua.edu.cn [Department of Precision Instrument, Tsinghua University, Beijing, 100084 (China); Gillen, R. [Institut für Festkörperphysik. Technische Universität Berlin. Hardenbergstr. 36, 10623 Berlin (Germany); Robertson, J., E-mail: jr214@cam.ac.uk [Engineering Department, University of Cambridge, Cambridge CB2 1PZ (United Kingdom)

2016-06-15

The screened exchange (sX) hybrid functional has been widely used in computational material science. Although it has widely been studied in bulk systems, less is known about its functional behavior in surface systems which are crucial to many technologies such as materials synthesis and nano-electronic devices. Assessing the screening dependent functional behaviors in the surface systems is therefore important for its application in such systems. In this work, we investigate the screening effects of the sX in CO adsorption on Pt(111) surface. The differences between the sX and Heyd-Scuseria-Ernzerhof (HSE06) hybrid functionals, and the effects of screening parameters are studied. The screening has two effects: first, the HOMO-LUMO gap is screening dependent. This affects the site preference most significantly. In this work, atop adsorption of CO/Pt(111) is predicted by the hybrid functionals with screened exchange potential. The sX(1.44) gives the largest HOMO-LUMO gap for the isolated CO molecule. The adsorption energy difference between the atop and fcc site is also the largest by the sX(1.44) which is explained by the reduced metal d states to the CO 2π* state back-donation, with stronger effect for the fcc adsorption than for the atop adsorption; second, the adsorption energy is screening dependent. This can be seen by comparing the sX(2.38) and HSE06 which have different screening strengths. They show similar surface band structures for the CO adsorption but different adsorption energies, which is explained by the stronger CO 5σ state to the metal d states donation or the effectively screened Pauli repulsion. This work underlines the screening strength as a main difference between sX and HSE06, as well as an important hybrid functional parameter for surface calculation.

Development and characterisation of a novel composite electrode material consisting of poly(3,4-ethylenedioxythiophene) including Au nanoparticles

International Nuclear Information System (INIS)

Zanardi, C.; Terzi, F.; Pigani, L.; Heras, A.; Colina, A.; Lopez-Palacios, J.; Seeber, R.

2008-01-01

Composite material consisting of poly(3,4-ethylenedioxythiophene) (PEDOT), including Au nanoparticles encapsulated by N-dodecyl-N,N-dimethyl-3-ammonium-1-propanesulphonate (SB12) is synthesised by constant-current method on ITO glass, in aqueous medium, leading to an electrode coating. The synthesis process is followed by UV-vis spectroelectrochemistry, both in normal-beam and in parallel-beam configurations. Under the same experimental conditions PEDOT is also synthesised by electropolymerisation only in the presence of LiClO 4 supporting electrolyte, as well in solutions also containing SB12. The data relative to the electrosynthesis of the three materials are compared. The composite material based on the conductive polymer matrix including Au nanoparticles has been characterised by SEM, TEM, ICP, Raman and UV-vis spectroscopies. The behaviour of the three different electrode coatings with respect to p-doping process has been studied by conventional electrochemical techniques and by potentiostatic and potentiodynamic UV-vis spectroelectrochemical methods. Conclusions are drawn out about the effect of the presence of the surfactant and of Au nanoparticles on the electrochemical properties of the electrode system

Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations

DEFF Research Database (Denmark)

Skulason, Egill; Tripkovic, Vladimir; Björketun, Mårten

2010-01-01

charged Pt(111) slab and solvated protons in up to three water bilayers is considered and reaction energies and activation barriers are determined by using a newly developed computational scheme where the potential can be kept constant during a charge transfer reaction. We determine the rate limiting...... reaction on Pt(111) to be Tafel−Volmer for HOR and Volmer−Tafel for HER. Calculated rates agree well with experimental data. Both the H adsorption energy and the energy barrier for the Tafel reaction are then calculated for a range of metal electrodes, including Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Ru, Re......, W, Mo, and Nb, different facets, and step of surfaces. We compare the results for different facets of the Pt electrode to experimental data. Our results suggest that the most important parameter for describing the HOR or the HER activity of an electrode is its binding free energy of H. We present...

Sensitivity of photoelectron diffraction to conformational changes of adsorbed molecules: Tetra-tert-butyl-azobenzene/Au(111

Directory of Open Access Journals (Sweden)

A. Schuler

2017-01-01

Full Text Available Electron diffraction is a standard tool to investigate the atomic structure of surfaces, interfaces, and adsorbate systems. In particular, photoelectron diffraction is a promising candidate for real-time studies of structural dynamics combining the ultimate time resolution of optical pulses and the high scattering cross-sections for electrons. In view of future time-resolved experiments from molecular layers, we studied the sensitivity of photoelectron diffraction to conformational changes of only a small fraction of molecules in a monolayer adsorbed on a metallic substrate. 3,3′,5,5′-tetra-tert-butyl-azobenzene served as test case. This molecule can be switched between two isomers, trans and cis, by absorption of ultraviolet light. X-ray photoelectron diffraction patterns were recorded from tetra-tert-butyl-azobenzene/Au(111 in thermal equilibrium at room temperature and compared to patterns taken in the photostationary state obtained by exposing the surface to radiation from a high-intensity helium discharge lamp. Difference patterns were simulated by means of multiple-scattering calculations, which allowed us to determine the fraction of molecules that underwent isomerization.

Top-Contact Pentacene-Based Organic Thin Film Transistor (OTFT) with N, N'-Bis(3-Methyl Phenyl)- N, N'-Diphenyl Benzidine (TPD)/Au Bilayer Source-Drain Electrode

Science.gov (United States)

Borthakur, Tribeni; Sarma, Ranjit

2018-01-01

A top-contact Pentacene-based organic thin film transistor (OTFT) with N, N'-Bis (3-methyl phenyl)- N, N'-diphenyl benzidine (TPD)/Au bilayer source-drain electrode is reported. The devices with TPD/Au bilayer source-drain (S-D) electrodes show better performance than the single layer S-D electrode OTFT devices. The field-effect mobility of 4.13 cm2 v-1 s-1, the on-off ratio of 1.86 × 107, the threshold voltage of -4 v and the subthreshold slope of .27 v/decade, respectively, are obtained from the device with a TPD/Au bilayer source-drain electrode.

Preparation of Atomically Flat Si(111)-H Surfaces in Aqueous Ammonium Fluoride Solutions Investigated by Using Electrochemical, In Situ EC-STM and ATR-FTIR Spectroscopic Methods

International Nuclear Information System (INIS)

Bae, Sang Eun; Oh, Mi Kyung; Min, Nam Ki; Paek, Se Hwan; Hong, Suk In; Lee, Chi-Woo J.

2004-01-01

Electrochemical, in situ electrochemical scanning tunneling microscope (EC-STM), and attenuated total reflectance-FTIR (ATR-FTIR) spectroscopic methods were employed to investigate the preparation of atomically flat Si(111)-H surface in ammonium fluoride solutions. Electrochemical properties of atomically flat Si(111)-H surface were characterized by anodic oxidation and cathodic hydrogen evolution with the open circuit potential (OCP) of ca. .0.4 V in concentrated ammonium fluoride solutions. As soon as the natural oxide-covered Si(111) electrode was immersed in fluoride solutions, OCP quickly shifted to near .1 V, which was more negative than the flat band potential of silicon surface, indicating that the surface silicon oxide had to be dissolved into the solution. OCP changed to become less negative as the oxide layer was being removed from the silicon surface. In situ EC-STM data showed that the surface was changed from the initial oxide covered silicon to atomically rough hydrogen-terminated surface and then to atomically flat hydrogen terminated surface as the OCP moved toward less negative potentials. The atomically flat Si(111)-H structure was confirmed by in situ EC-STM and ATR-FTIR data. The dependence of atomically flat Si(111)-H terrace on mis-cut angle was investigated by STM, and the results agreed with those anticipated by calculation. Further, the stability of Si(111)-H was checked by STM in ambient laboratory conditions

Effect of Au proximity on the LSMO surface: An ab initio study

International Nuclear Information System (INIS)

Petti, D.; Stroppa, A.; Picozzi, S.; Brivio, S.; Cantoni, M.; Bertacco, R.

2012-01-01

The effect of the proximity of Au on the electronic and magnetic properties of La 0.66 Sr 0.33 MnO 3 (LSMO) has been investigated by means of ab initio calculations within the density-functional theory. The calculations show an orbital reconstruction of the interfacial Mn, which is due more to the presence of a discontinuity rather than to a real chemical interaction with Au atoms. In fact, the same orbital reconstruction is found in the free LSMO surface. In both cases of Au/LSMO and LSMO surface, the Mn magnetic moments change very little with respect to the bulk case. In general, the calculations show a negligible influence of the Au atomic layer on LSMO at an ideal interface, with the LSMO surface magnetic and electronic properties essentially unchanged. - Highlights: ► Three structures considered: bulk LSMO, Au/LSMO and vacuum LSMO interfaces. ► At the two interfaces the formation of a discontinuity creates an orbital ordering. ► DFT calculations point toward an enhancement of the magnetization at the interface. ► Negligible chemical interaction with gold is seen for a 2D ideal interface. ► Crucial role of the 3D nature of Au on LSMO in depressing LSMO magnetic properties.

Sensing CA 15-3 in point-of-care by electropolymerizing O-phenylenediamine (oPDA on Au-screen printed electrodes.

Directory of Open Access Journals (Sweden)

Rui S Gomes

Full Text Available This work presents an alternative device for cancer screening in liquid biopsies. It combines a biomimetic film (i with electrochemical detection (ii. The biomimetic film (i was obtained by electro-polymerizing amine-substituted benzene rings around a CA 15-3 target. This protein target was previously adsorbed on a gold (Au support and incubated in charged monomers (4-Styrenesulfonate sodium and 3-Hydroxytyraminium chloride. The protein was further eliminated by enzymatic activity, leaving behind vacant sites for subsequent rebinding. Electrochemical detection (ii was achieved on an Au working electrode, designed on commercial screen-printed electrodes. Raman spectroscopy, atomic force microscopy and ellipsometric readings were used to follow the chemical modification of the Au surface. The ability of the material to rebind CA15-3 was monitored by electrochemical techniques. The device displayed linear responses to CA15-3 ranging from 0.25 to 10.00 U/mL, with detection limits of 0.05 U/mL. Accurate results were obtained by applying the sensor to the analysis of CA15-3 in PBS buffer and in serum samples. This biosensing device displayed successful features for the detection of CA 15-3 and constitutes a promising tool for breast cancer screening procedures in point-of-care applications. Moreover, its scale-up seems feasible as it contains a plastic antibody assembled in situ, in less than 1 minute, and the analysis of serum takes less than 30 minutes.

Amperometric Immunosensor for Carbofuran Detection Based on MWCNTs/GS-PEI-Au and AuNPs-Antibody Conjugate

Directory of Open Access Journals (Sweden)

Xiangyou Wang

2013-04-01

Full Text Available In this paper, an amperometric immunosensor for the detection of carbofuran was developed. Firstly, multiwall carbon nanotubes (MWCNTs and graphene sheets-ethyleneimine polymer-Au (GS-PEI-Au nanocomposites were modified onto the surface of a glass carbon electrode (GCE via self-assembly. The nanocomposites can increase the surface area of the GCE to capture a large amount of antibody, as well as produce a synergistic effect in the electrochemical performance. Then the modified electrode was coated with gold nanoparticles-antibody conjugate (AuNPs-Ab and blocked with BSA. The monoclonal antibody against carbofuran was covalently immobilized on the AuNPs with glutathione as a spacer arm. The morphologies of the GS-PEI-Au nanocomposites and the fabrication process of the immunosensor were characterized by X-ray diffraction (XRD, ultraviolet and visible absorption spectroscopy (UV-vis and scanning electron microscopy (SEM, respectively. Under optimal conditions, the immunosensor showed a wide linear range, from 0.5 to 500 ng/mL, with a detection limit of 0.03 ng/mL (S/N = 3. The as-constructed immunosensor exhibited notable performance features such as high specificity, good reproducibility, acceptable stability and regeneration performance. The results are mainly due to the excellent properties of MWCNTs, GS-PEI-Au nanocomposites and the covalent immobilization of Ab with free hapten binding sites for further immunoreaction. It provides a new avenue for amperometric immunosensor fabrication.

First-principle study of Mg adsorption on Si(111) surfaces

International Nuclear Information System (INIS)

Min-Ju, Ying; Ping, Zhang; Xiao-Long, Du

2009-01-01

We have carried out first-principle calculations of Mg adsorption on Si(111) surfaces. Different adsorption sites and coverage effects have been considered. We found that the threefold hollow adsorption is energy-favoured in each coverage considered, while for the clean Si(111) surface of metallic feature, we found that 0.25 and 0.5 ML Mg adsorption leads to a semiconducting surface. The results for the electronic behaviour suggest a polarized covalent bonding between the Mg adatom and Si(111) surface. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

Piperidine adsorption on two different silver electrodes: A combined surface enhanced Raman spectroscopy and density functional theory study

International Nuclear Information System (INIS)

Hao Yanling; Fang Yan

2007-01-01

The surface enhanced Raman scattering (SERS) spectra of piperidine in silver colloid solution, on roughened silver electrode and on roughened silver electrode modified with silver nanoparticles were studied, and the high-quality SERS spectra of piperidine on roughened silver electrode modified with silver nanoparticles were obtained for the first time. Surface selection rules derived from the EM enhancement model were employed to deduce piperidine orientations on the different surfaces. On the basis of this, two models of piperidine adsorbed on the surface of the silver nanoparticles were built, and DFT-B3PW91/LanL2dz was applied to calculate the Raman frequencies. It proves that, at higher potential values, the piperidine is perpendicularly standing on the roughened silver electrode surface though its lone-electron pair, but in silver colloid solution and on the silver nanoparticles modified silver electrode the piperidine molecular lies flat on the silver surface. In the meantime, the potential dependent SERS of piperidine on the modified electrode were studied

Metal-like Band Structures of Ultrathin Si {111} and {112} Surface Layers Revealed through Density Functional Theory Calculations.

Science.gov (United States)

Tan, Chih-Shan; Huang, Michael H

2017-09-04

Density functional theory calculations have been performed on Si (100), (110), (111), and (112) planes with tunable number of planes for evaluation of their band structures and density of states profiles. The purpose is to see whether silicon can exhibit facet-dependent properties derived from the presence of a thin surface layer having different band structures. No changes have been observed for single to multiple layers of Si (100) and (110) planes with a consistent band gap between the valence band and the conduction band. However, for 1, 2, 4, and 5 Si (111) and (112) planes, metal-like band structures were obtained with continuous density of states going from the valence band to the conduction band. For 3, 6, and more Si (111) planes, as well as 3 and 6 Si (112) planes, the same band structure as that seen for Si (100) and (110) planes has been obtained. Thus, beyond a layer thickness of five Si (111) planes at ≈1.6 nm, normal semiconductor behavior can be expected. The emergence of metal-like band structures for the Si (111) and (112) planes are related to variation in Si-Si bond length and bond distortion plus 3s and 3p orbital electron contributions in the band structure. This work predicts possession of facet-dependent electrical properties of silicon with consequences in FinFET transistor design. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The phases of Pb/Ge(111): A surface X-ray diffraction study

International Nuclear Information System (INIS)

Grey, F.

1988-03-01

This report describes the results of several surface X-ray diffraction measurements of a chemisorbed overlayer of Pb on the Ge(111) surface. Three phases of Pb/Ge(111) exist in the monolayer regime: the α- and β-phases with a √3x√3R30 0 unit cell, and a high-temperature 1x1 phase. In the 1x1 phase of Pb/Ge(111), isotropic X-ray scattering is observed consistent with a two-dimensional liquid phase. Measurements of the integer-order Bragg reflections through the √3x√3R30 0 →1x1 transition confirm the liquid-like nature of the 1x1 phase, and show that the liquid layer is modulated by the periodic potential of the substrate. By measuring variations of the (2/3,2/3) surface Bragg reflection from the √3x√3R30 0 phase as a function of temperature and coverage, a simple phase diagram for Pb/Ge(111) is deduced. Below 1/3ML (where 1 ML is one Pb atom per Ge surface atom) the α-phase coexists with the 1x1 phase. Between 1/3ML and 4/3ML, α- and β-phases form a two-phase system displaying phase separation. Analogies with simple theoretical phase diagrams are emphasized. (orig.) With 11 tabs., 40 figs., 67 refs

Atomic structure and composition of the yttria-stabilized zirconia (111) surface.

Science.gov (United States)

Vonk, Vedran; Khorshidi, Navid; Stierle, Andreas; Dosch, Helmut

2013-06-01

Anomalous and nonanomalous surface X-ray diffraction is used to investigate the atomic structure and composition of the yttria-stabilized zirconia (YSZ)(111) surface. By simulation it is shown that the method is sensitive to Y surface segregation, but that the data must contain high enough Fourier components in order to distinguish between different models describing Y/Zr disorder. Data were collected at room temperature after two different annealing procedures. First by applying oxidative conditions at 10 - 5  mbar O 2 and 700 K to the as-received samples, where we find that about 30% of the surface is covered by oxide islands, which are depleted in Y as compared with the bulk. After annealing in ultrahigh vacuum at 1270 K the island morphology of the surface remains unchanged but the islands and the first near surface layer get significantly enriched in Y. Furthermore, the observation of Zr and oxygen vacancies implies the formation of a porous surface region. Our findings have important implications for the use of YSZ as solid oxide fuel cell electrode material where yttrium atoms and zirconium vacancies can act as reactive centers, as well as for the use of YSZ as substrate material for thin film and nanoparticle growth where defects control the nucleation process.

A scanning tunneling microscopy study of the electronic and spin states of bis(phthalocyaninato)terbium(iii) (TbPc2) molecules on Ag(111).

Science.gov (United States)

Ara, Ferdous; Qi, Zhi Kun; Hou, Jie; Komeda, Tadahiro; Katoh, Keiichi; Yamashita, Masahiro

2016-10-25

In this article, we investigate a single molecule magnet bis(phthalocyaninato)terbium(iii) (TbPc 2 ) molecule film by using low temperature STM. In order to investigate the effect of molecule-substrate interaction on the electronic and spin properties of the adsorbed molecule, we tune the molecule-substrate coupling by switching the substrate between Au(111) and Ag(111), the latter of which provides stronger interaction with the molecule than the former. Despite the enhanced chemical reactivity of the Ag(111) surface compared with Au(111), a well-organized pseudo-square film is formed. In addition, a checker-board type contrast variation is identified, which is well explained by the existence of two types of molecules whose rotational angle between the top and bottom Pc is θ = 45° (bright molecule) and θ = 30° (dark molecule). The expected stronger molecule-substrate interaction, however, appears as an intriguing dI/dV mapping image which reveals the spatial distribution of the density of states (DOS). We identify the contrast reversal in the dI/dV mapping for the molecules of θ = 45° and θ = 30° at the sample voltages of V = 0.7 eV and 1.1 eV. Combined with the density functional theory (DFT) calculation, we attribute this change to the shift of an electronic state due to the rotation of the mutual angle between the top and bottom Pc. For the spin behavior, we previously observed a Kondo resonance for the TbPc 2 molecule adsorbed on the Au(111) surface. On the Ag(111) surface, the Kondo resonance is hardly observed, which is due to the annihilation of the π radical spin by the charge transfer from the substrate to the molecule. Instead we observe a Kondo peak for the molecule on the second layer, for which the spin recovers due to the reduction of the coupling with the substrate. In addition, when a magnetic field of 2 T normal to the surface is applied, the second layer molecule shows a sharp dip at the Fermi level. We attribute this to the inelastic

Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni

Energy Technology Data Exchange (ETDEWEB)

López-Moreno, S., E-mail: sinlopez@uacam.mx [Centro de Investigación en Corrosión, Universidad Autónoma de Campeche, Av. Héroe de Nacozari 480, Campeche, Campeche 24029 (Mexico); Romero, A. H. [Physics Department, West Virginia University, Morgantown, West Virginia 26506-6315 (United States)

2015-04-21

Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O{sub 2} molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered.

Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni

Science.gov (United States)

López-Moreno, S.; Romero, A. H.

2015-04-01

Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O2 molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered.

Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni

International Nuclear Information System (INIS)

López-Moreno, S.; Romero, A. H.

2015-01-01

Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O 2 molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered

Clean Os(0001) electronic surface states: A first-principle fully relativistic investigation

Science.gov (United States)

Urru, Andrea; Dal Corso, Andrea

2018-05-01

We analyze the electronic structure of the Os(0001) surface by means of first-principle calculations based on Fully Relativistic (FR) Density Functional Theory (DFT) and a Projector Augmented-Wave (PAW) approach. We investigate surface states and resonances analyzing their spin-orbit induced energy splitting and their spin polarization. The results are compared with previously studied surfaces Ir(111), Pt(111), and Au(111). We do not find any surface state in the gap similar to the L-gap of the (111) fcc surfaces, but find Rashba split resonances that cross the Fermi level and, as in the recently studied Ir(111) surface, have a characteristic downward dispersion. Moreover, for some selected surface states we study the spin polarization with respect to k∥, the wave-vector parallel to the surface. In some cases, such as the Rashba split resonances, the spin polarization shows a smooth behavior with slow rotations, in others the rotation is faster, due to mixing and anti-crossing of the states.

Chitosan coated on the layers' glucose oxidase immobilized on cysteamine/Au electrode for use as glucose biosensor.

Science.gov (United States)

Zhang, Yawen; Li, Yunqiu; Wu, Wenjian; Jiang, Yuren; Hu, Biru

2014-10-15

A glucose biosensor was developed via direct immobilization of glucose oxidase (GOD) by self-assembled cysteamine monolayer on Au electrode surface followed by coating chitosan on the surface of electrode. In this work, chitosan film was coated on the surface of GOD as a protection film to ensure the stability and biocompatibility of the constructed glucose biosensor. The different application ranges of sensors were fabricated by immobilizing varied layers of GOD. The modified surface film was characterized by a scanning electron microscope (SEM) and the fabrication process of the biosensor was confirmed through electrochemical impedance spectroscopy (EIS) of ferrocyanide. The performance of cyclic voltammetry (CV) in the absence and presence of 25 mM glucose and ferrocenemethanol showed a diffusion-controlled electrode process and reflected the different maximum currents between the different GOD layers. With the developed glucose biosensor, the detection limits of the two linear responses are 49.96 μM and 316.8 μM with the sensitivities of 8.91 μA mM(-1)cm(-2) and 2.93 μA mM(-1)cm(-2), respectively. In addition, good stability (up to 30 days) of the developed biosensor was observed. The advantages of this new method for sensors construction was convenient and different width ranges of detection can be obtained by modified varied layers of GOD. The sensor with two layers of enzyme displayed two current linear responses of glucose. The present work provided a simplicity and novelty method for producing biosensors, which may help design enzyme reactors and biosensors in the future. Copyright © 2014 Elsevier B.V. All rights reserved.