The potentials of zero charge of Pd(1 1 1) and thin Pd overlayers on Au(1 1 1)

The potential of zero charge (pzc) of Pd(1 1 1) has been determined in dilute NaF solutions by measuring the Gouy–Chapman minimum of the double-layer capacity. For a massive Pd(1 1 1) single crystal electrode a pzc of −0.12 V vs. SCE has been found. The corresponding values for thin Pd(1 1 1) overlayers on Au(1 1 1) have also been determined. While the pzc of the first, pseudomorphic Pd layer on Au(1 1 1) is −0.09 V vs. SCE, the pzc of a five monolayers thick Pd film on Au(1 1 1) is practically identical to the pzc of the massive Pd(1 1 1) electrode. By comparing pzc's and work functions for Au(1 1 1) and Pd(1 1 1), the dipole contribution to the potential drop across the Pd(1 1 1)/water interface is estimated.     

Spontaneous deposition of Sn on Au(1 1 1). An in situ STM study

The tin adlayer formed by spontaneous deposition on Au(1 1 1) was characterized by cyclic voltammetry and in situ scanning tunneling microscopy (STM) in sulphuric acid solution. Cyclic voltammetry measurements showed oxidation peaks in the potential range −0.60 ⩽ E/V vs SSE ⩽ 0, which can be ascribed to the dissolution of the Sn adsorbed layer. STM images of the Au(1 1 1)/Sn modified surface showed that tin nucleated both on step edges and on the flat terraces forming two-dimensional islands. The anodic polarization of this modified surface produced the gradual dissolution of the Sn adlayer which was evidenced by the formation of some holes and the reduction of the initial terraces to many small islands. STM images with atomic resolution obtained on these islands displayed an hexagonal expanded atomic structure. After the anodic stripping of this Sn adsorbed layer the images exhibited the typical Au(1 1 1) terraces with a (1 × 1) atomic structure. However, at more anodic potentials another dissolution process was observed producing noticeable changes on the surface morphology which could be ascribed to the dissolution of a Au–Sn surface alloy.     

The influence of chloride on the initial anodic dissolution of Cu3Au(1 1 1)

We report a detailed in situ X-ray diffraction study of the influence of chloride on the atomic structure evolution at the solid-electrolyte interface during the selective dissolution of Cu from a Cu₃Au(1 1 1) surface immersed in 0.1 M H₂SO₄. We disclose that the formation of the initial ultrathin Au-rich (1 1 1) with an inverted stacking sequence, as recently observed at Cu₃Au(1 1 1) in contact with pure 0.1 M H₂SO₄, is strongly influenced by adding 5 mM HCl. The main finding is a negative shift of about 150 mV of the critical potential at which the ultra-thin Au-rich layer transforms into thicker Au islands. The presented results support the view that it is not a thermodynamic driving force, but rather the rate of surface diffusion that dominates the formation of the structures of the metallic layer.     

Potentiodynamic electrochemical impedance spectroscopy of lead upd on polycrystalline gold and on selenium atomic underlayer

Pb upd on polycrystalline Au and on Au coated with Se atomic layer was investigated by potentiodynamic electrochemical impedance spectroscopy. Faradaic and double layer responses have disclosed two distinct stages in Pb upd on Au: a partly irreversible stage, attributed to formation and growth of Pb 2D islands, and a reversible phase transition in the final stage of a monolayer deposition. The completion of a continuous monolayer formation in the potential scan was signalised by a sharp minimum in double layer pseudocapacitance Q_dl. Pb²⁺ reduction, which was monitored concurrently by parameters of Faradaic response, continued shortly after the Q_dl minimum and showed sharp maxima of adsorption capacitance and inverse Warburg constant at 40 mV below Q_dl minimum. This was explained by surface free energy minimisation that forced continuous atomic layer formation with inclusion of some lead cations into Pb monolayer. The two-stage Pb upd transformed into a single-stage strongly irreversible upd as a result of Se atomic underlayer deposition on Au.     

In situ and real-time surface differential diffraction (SDD) study of Cd underpotential deposition on Au(1 1 1)

In situ and real-time surface differential diffraction (SDD) has been used to study the underpotential deposition (UPD) of Cd on Au(1 1 1) in sulfuric acid media. Comparison of SDD results in sulfate electrolytes with and without the presence of Cd²⁺ ions reveals that the surface reconstruction associated with the sulfate adsorption and desorption dominates the structural effect. It is also found that the reconstructed gold surface is stable upon Cd UPD process. In the initial stages of UPD, Cd atoms bind to the surface in bridge sites. This is followed by an adlayer structure with Cd adsorption in threefold hollow sites before Au/Cd intermixing takes place.     

Modelling of benzene-1,4-dithiol on a Au(1 1 1) surface

The bonding of benzene-1,4-dithiol to a Au(1 1 1) surface is studied using a Au₂₅–SC₆H₄SH model. We find that the most favorable structure has the S directly above an Au atom, i.e., an on-top site. If the molecule is constrained to be perpendicular to the surface, the on-top site is the least favorable site and the threefold hollow is the most favorable one.     

Quasi-reversible two-electron reduction of oxygen at gold electrodes modified with a self-assembled submonolayer of cysteine

The electrochemical reduction of molecular oxygen (O₂) has been performed at gold electrodes modified with a submonolayer of a self-assembly (sub-SAM/Au) of a thiol compound (typically cysteine (CYST)) in O₂-saturated 0.5 M KOH. At bare gold electrode O₂ reduction reaction proceeds irreversibly, while this reaction is totally hindered at gold electrodes with a compact structure of CYST over its surface. The partial reductive desorption of the compact CYST monolayer was achieved by controlling the potential of the CYST/Au electrode, leading to the formation of a submonolayer coverage of the thiol compound over the Au electrode surface (sub-SAM/Au), at which the CYST molecules selectively block the Au(1 0 0) and Au(1 1 0) fractions (the so-called rough domains) of the polycrystalline Au while the Au(1 1 1) component (the so-called smooth domains) remains bare (i.e., uncovered with CYST). This sub-SAM/Au electrode extraordinarily exhibits a quasi-reversible two-electron reduction of molecular oxygen (O₂) in alkaline medium with a peak separation (ΔE_p) between the cathodic and anodic peak potentials (E_p^c,E_p^a) of about 60 mV. The ratio of the anodic current to the cathodic one is close to unity. The formal potential (E^o′) of this reaction is found to equal −150 mV vs. Ag/AgCl/KCl(sat.).     

Electronic structure of the Au–Si(1 1 1) interface as a function of Au coverage

We have investigated the Au–Si(1 1 1) interface as a function of the Au coverage by the core-level photoemission spectroscopy. With increasing the Au coverage, the spectral features in the Si 2p core-level changed remarkably and some fine structures in both Si 2p and Au 4f spectra were observed. Based on the curve fitting analysis, the Si 2p and Au 4f spectra at more than 20 Å Au coverage were decomposed into three chemically different components, respectively. The assignments of their components were performed. In addition, we have compared these results for the Au–Si(1 1 1) interface with our previous study for the Au–Si(1 0 0) interface. It was found that the electronic structures for the Au–Si(1 1 1) interface is essentially identical to those of the Au–Si(1 0 0) interface except at the initial Au deposition.     

Highly ordered adlayers of three calix[4]arene derivatives on Au(1 1 1) surface in HClO4 solution: in situ STM study

Highly ordered adlayers of three calix[4]arene derivatives have been prepared on Au(1 1 1) surface in HClO₄ solution. The adlayer structures are characterized by in situ scanning tunneling microscopy (STM). High-resolution STM images reveal the molecular orientation and packing arrangement in the ordered adlayers. All the molecules are upright on Au(1 1 1) surface in pinched cone conformation. The structural difference of these molecules is proposed to be from the different functional groups at the upper and lower positions. The structural models are tentatively proposed for three ordered adlayers.     

Electrocatalytic oxidation of sugars on silver-UPD single crystal gold electrodes in alkaline solutions

A highly catalytic system for sugar oxidation in alkaline media is presented, for the first time, in which glucose oxidation takes place at ca. −0.44 V (vs. Ag|AgCl). Modification of Au(1 1 1) single crystal surface by under potential deposition (UPD) was carried out for a variety of metals and catalytic effect for sugar oxidation has been studied in 0.1 M NaOH. UPD of Ag ad-atoms on Au electrodes were of the best catalytic activity compared to other metals (Cu, Co, Ru, Cd, Ir, and Pt, etc.). For aldose type monosaccharide studied (glucose, mannose and xylose) as well as for aldose-containing disaccharides (maltose and lactose), one significant oxidation peak was obtained, however, no significant oxidation current was observed for disaccharides like sucrose. Gluconolactone and mannolactone gave no oxidation current at negative potentials at which glucose was oxidized, indicating no more than two-electron oxidation took place. With Ag ad-atoms coverage of ca. 0.3 monolayer leads to a positive catalytic effect expressed through a negative shift of ca. 0.14 V (glucose case) on the oxidation potential and a slight increase in peak current. At the Au(1 0 0) surface similar results to those at an Au(1 1 1) electrode were also observed.     

EC-STM observation on electrochemical response of fluidic phospholipid monolayer on Au(1 1 1) modified with 1-octanethiol

Electrochemical scanning tunneling microscopy (EC-STM) was applied to observe phospholipid layers over thiol-modified gold substrates as a model biological cell membrane. On a monolayer of 1-octanethiol on Au (1 1 1), a synthetic lipid, 1,2-dihexanoyl-sn-glycero-3-phosphocholine, was introduced in a neutral 0.05 M NH₄ClO₄ buffer solution. The lipid molecules formed a fluidic layer at 0.0 V vs. RHE of the substrate electrode potential. By cycling the electrode potential between +0.2 V and −0.2 V, the lipid layer reversibly changed over between the fluidic phase and a striped/grainy structure. This structural change might involve partial decomposition and oligomerization of phospholipids. This method will contribute for molecular biology by revealing the nanometer-scale structure of cell membrane.     

Evolution of microstructure and crack pattern in NiO thin films under 200 MeV Au ion irradiation

NiO thin films grown on Si (100) substrate by electron beam evaporation method and sintered at 700 °C were irradiated with 200 MeV Au¹⁵⁺ ions. The fcc structure of the sintered films was retained up to the highest fluence (1×10¹³ ions cm^?2) of irradiation. However the microstructure of the pristine film underwent a considerable modification with increasing ion fluence. 200 MeV Au ion irradiation led to compressive stress generation in NiO medium. The diameter of the stressed region created by 200 MeV Au ions along the ion path was estimated from the variation of stress with ion fluence and found to be ～11.6 nm. The film surface started cracking when irradiated at and above the fluence of 3×10¹² ions cm^?2. Ratio of the fractal dimension of the cracked surface obtained at 200 MeV and 120 MeV (Mallick et al., 2010a) Au ions was compared with the ratio of the radii of ion tracks calculated based on Coulomb explosion and thermal spike models. This comparison indicated applicability of thermal spike model for crack formation.     

Structures and thermodynamic phase transitions for oxygen and silver oxide phases on Ag{1 1 1}

With density functional theory, we have examined oxygen adsorption at surface and subsurface sites of Ag{1 1 1}. The microscopic structure of Ag oxide epitaxed to Ag{1 1 1} has also been determined. In agreement with a recent scanning tunneling microscopy study, non-stoichiometric oxide growth is favoured over the previously assumed stoichiometric growth. An ab initio phase diagram for O on Ag{1 1 1} has been constructed from the adsorption free energy of the various O and Ag oxide phases. The key finding is that under real conditions for ethylene epoxidation the active catalyst is likely to be non-stoichiometric Ag oxide.     

In situ femtosecond spectroelectrochemistry of Au(1 1 1) in an aqueous chloride solution

In this paper we report the first in situ femtosecond spectroelectrochemistry experiment employing a broadband probe, allowing the measurement of ultrafast transient visible spectra with a fixed pump wavelength. We investigated in situ femtosecond transient reflectivity of a Au(1 1 1) electrode in contact with an aqueous KCl solution. The pump wavelength was set at 780 nm and a supercontinuum probe was employed, yielding ultrafast spectral information on the electron thermalisation dynamics in the range 450–650 nm. Electrochemical control allowed to investigate the dynamic response to different Cl^? adsorption conditions.     

A possible approach towards spin-polarized transport through single molecule magnets: Mn12 on Au(1 0 0)/Fe(1 0 0)/MgO(1 0 0)

The possibility to use the Au(1 0 0)/Fe(1 0 0)/MgO(1 0 0) system as a substrate for future spin-polarized transport measurements on Mn₁₂ single molecule magnets has been investigated by means of scanning tunneling microscopy and X-ray photoelectron spectroscopy at room temperature. In particular, the stability of the iron layer during a wet chemical preparation of Mn₁₂ monolayers was studied. The results demonstrate that Mn₁₂ can be deposited on Au(1 0 0)/Fe(1 0 0)/MgO(1 0 0) while preserving the metallic nature of the ferromagnetic iron layer which is required as a possible source of spin-polarized electrons in future studies.     

Comparative theoretical study of the structure and bonding of propyne on the Pt(1 1 1) and Pd(1 1 1) surfaces

The interaction of propyne with the Pt(1 1 1) and Pd(1 1 1) surfaces has been studied by means of the generalised gradient approach of density functional theory using periodic slab models. For both surfaces, the most stable adsorption mode of propyne is di-σ/π mode where the hydrocarbon is σ-bonded to two metal atoms with some additional π bonding to a third adjacent surface atom. The adsorption geometry is a highly distorted propyne with the C₁ and C₂ in a nearly sp² hybridisation. Two equivalent surface structures have been found on Pt and Pd. These correspond to the adsorption on the fcc or hcp hollow sites. The adsorption energies on Pt(1 1 1) and Pd(1 1 1) are predicted to be ∼−197 and −161 kJ mol⁻¹, respectively. The electronic factors that control the chemisorption have been analysed by means of the projected density of states.     

Application of organic monolayers formed on Si(1 1 1): possibilities for nanometer-scale patterning

The modification of hydrogen-terminated Si(1 1 1) wafer surfaces was reproduced by previously reported methods of the electrolysis of para-substituted benzendiazonium salts and the Grignard reaction with various alkyl moieties. The electrolysis methods formed partially ordered two-dimensional monolayers, which were however obscured by precipitation of by-products. The Grignard reaction deposited a monolayer of moieties of alkyl groups randomly arranged, which are more suitable for surface passivation. Aiming for the application to nanometer-scale monolayer patterning of the Si(1 1 1) wafer surface, the organic-monolayer-covered Si(1 1 1) surfaces were subjected to electron beam bombardment. After electron bombardment with ambient O₂ or H₂O introduced, adsorption of oxygen was observed within the beam spot. By immersing the bombarded specimen into an aqueous NiSO₄+(NH₄)₂SO₄ solution, the oxygen-deposited portions selectively included Ni atoms. This will be useful in constructing nanometer-scale metallic structures over Si wafer surfaces.     

In situ study of nitrobenzene grafting on Si(1 1 1)-H surfaces by infrared spectroscopic ellipsometry

The binding of nitrobenzene (NB) molecules from a solution of 4-nitrobenzene-diazonium-tetrafluoroborate on a Si(1 1 1)-H surface was investigated during the electrochemical processing in diluted sulphuric acid by means of infrared spectroscopic ellipsometry (IR-SE). The grafting was monitored by an increase in specific IR absorption bands due to symmetric and anti-symmetric NO₂ stretching vibrations in the 1400–1700 cm^?1 regime. The p- and s-polarized reflectances were recorded within 20 s for each spectrum only. NB molecules were detected when bonded to the Si(1 1 1) surface but not in the 2 mM solution itself. Oxide formation on the NB grafted Si surface was observed after drying in inert atmosphere and not during the grafting process in the aqueous solution.     

Adsorption of alkali metals on Ge(0 0 1)(2 × 1) surface

Ab initio total energy calculations have been performed for Na, K and Rb adsorption on Ge(0 0 1)(2 × 1) surface. It was found that the adsorption site of AM is AM size dependent. Structural analysis showed that the Ge–Ge dimer bond becomes stronger with increasing AM size. As the coverage increases from 0.5 to 1 ML it turns out that no depolarization effect occurs upon Na adsorption, while this effect becomes more important with increasing AM size. We also found that for all adsorption systems investigated the germanium surface is metallic and semiconducting for the coverage of 0.5 and 1 ML, respectively.