Ordered arrays of semi-crown ligands on an Au(111) electrode surface: in situ STM study

Self-organized systems have attracted much at-tention due to their potential applications in nano- technology as a bottom-up?approach for the con-struction of molecule-scale devices and nanostruc-tures[1—4]. Beyond the self-assembly of small molecu-lar building blocks, Schnherr et al. recently suc-ceeded in arranging the rosette supramolecular nanos-tructures in two dimensions on HOPG[5,6]. Moreover, interest has tremendously increased in the su-pramolecular structures via coordination-dr…     

Atomic structures and dynamics of a Cu(100) electrode in dilute hydrobromic acid: An in situ STM study

The surface electrochemistry of Cu(100) in 10 mM hydrobromic acid electrolyte has been studied by means of cyclic voltammetry and in situ STM. In the potential range between the onset of the anodic copper dissolution at positive and the hydrogen evolution at negative electrode potentials, the CV of Cu(100) in 10 mM HBr is characterized only by the double-layer charge. Within this potential regime a highly ordered (√2×√2)R45°-superstructure is seen in the STM experiments assigned to specifically adsorbed bromide anions. No desorption of the bromide adlayer has been found in these STM experiments even at extremely negative potentials at the onset of hydrogen evolution. Therefore the bromide desorption potential is concluded to lie within the potential regime of massive hydrogen evolution at even more negative potentials. Adsorbed bromide induces a drastic restructuring and faceting of the surface topography depending on the applied potential. The driving force of this process is the formation of thermodynamically favored copper steps aligned parallel to close packed 100 directions of the bromide adsorbate. Dynamic processes like copper dissolution and deposition are also strongly influenced by the geometry of the (√2×√2)R45° bromide adlayer. Corrosion as well as deposition of copper material follows the close packed 100 directions of the bromide adsorbate. For moderate reaction rates an additional anisotropy between the [001]- and [010]-direction is observed due to the nonequivalence of two different kinds of bromide stabilized copper steps. The origin of these two kinds of steps is the phase relation of close packed adsorbate rows of adjacent terraces. The deposition of copper material does not only start at the lower but unusually, also at the upper sites of step edges leading to the formation of microfacets. Not only the growth of monoatomically high islands is observed but also a double-layer and multilayer growth of copper.     

Schiff碱N-aete-N在Au(111)上自组装单分子膜的电化学及STM研究

利用电化学技术及扫描隧道显微镜(STM),于0.1mol/LHClO₄溶液中研究了Schiff碱N-aete-N在单晶Au(111)面上所形成的自组装单分子膜(SAMs)的电化学性质及结构.N-aete-N在Au(111)电极表面的吸附抑制了金的阳极氧化,同时使固/液界面双层电容明显降低.观察到N-aete-NSAMs的高分辨STM图像.N-aete-N分子在Au(111)表面上以(6×7)结构单胞呈二维有序排列,其表面浓度为5.5×10^-11mol/cm².     

Structure of thiocyanate adlayers on Rh(111): an in situ STM study

In situ scanning tunneling microscopy (STM) was used to examine the structure of thiocyanate adlayers specifically adsorbed on Rh(111) in solutions of potassium hydroxide and perchloric acid, both containing potassium thiocyanate (KSCN). An atomically flat terrace-step structure was consistently observed on Rh(111) surfaces prepared by the flame-annealing-quenching method. The Rh(111)-(1 × 1) atomic structure was discerned on the atomically flat terrace even in the alkaline solution. High-resolution STM images disclosed two different structures of the SCN⁻ adlayers, () and (2 × 2), in the alkaline and the acidic media, respectively. In each structure, an individual adsorbed SCN⁻ ion appeared as a single spot with a constant corrugation height in STM images, suggesting that SCN⁻ ions adsorbed predominantly with their S-ends at particular bonding sites on Rh(111). The difference in the adlayer structure in the two solutions can be attributed to the interaction between adsorbed SCN⁻ and coadsorbed K⁺ in the alkaline solution, and is different from that between adsorbed SCN⁻ and H⁺ in the acidic solution. Received: 26 February 1997 / Accepted: 3 March 1997     

Decorated Ru/Au(111) and Os/Au(111) surfaces: An in situ STM and electrochemistry study

The structure and reactivity of bimetallic electrodes obtained by spontaneous deposition of Ru and Os on Au(111) single-crystal surfaces are studied. In situ electrochemical STM and cyclic voltammetry are used to characterize a wide range of surface morphologies thus produced. The STM results on Ru/Au(111) demonstrate a pronounced step decoration, while a random distribution of Ru nuclei, quite uniform in size, occurs on terraces. Osmium deposits show a slight preference for deposition on steps, but it also occurs readily on terraces. However, many of the Os islands grow into multilayer heights. The coverage of the Au(111) by the deposited Ru or Os islands for a particular solution concentration depends on the deposition time. Nanostructures of Ru and Os are tested for catalytic behavior and correlated to CO oxidation activity as measured by CO stripping voltammetry. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 11, pp. 1385–1392. Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes,” October 18–22, 2005, Moscow. The text was submitted by the authors in English.     

Si(1 1 1)-(6 × 6)Au surface morphology and nucleation of Pb at low temperature

The morphologies of the Si(1 1 1)-(6 × 6)Au surface and the nucleation of Pb have been investigated at temperatures below room temperature using scanning tunnelling microscopy (STM). The STM scans of the clean Si(1 1 1)-(6 × 6)Au surface revealed exceptionally rich and strongly bias-dependent details within the unit cell. After deposition of about 0.01 ML of Pb(1 1 1), at temperatures above 180 K, the single Pb atoms formed a two-dimensional mesh with (6 × 6)-Au periodicity. In this early stage of deposition, the Pb atoms occupied predominantly one specific site of the (6 × 6) unit cell. The local symmetry of this site determined the further growth of the Pb layer. As a consequence, the structure of the Pb layer on Si(1 1 1)-(6 × 6)Au is rotated of 30° relative to that of the Pb layer on Si(1 1 1)-(7 × 7).     

Determination of insecticides in water using in situ halide exchange reaction-assisted ionic liquid dispersive liquid-liquid microextraction followed by high-performance liquid chromatography

A dispersive liquid-liquid microextraction (DLLME) method using in situ halide exchange reaction to form ionic liquid (IL) extraction phase was developed to determine four insecticides (i.e. methoxyfenozide, tetrachlorvinphos, thiamethoxam, and diafenthiuron) in water samples. The preconcentration procedure, followed by high-performance liquid chromatography and variable wavelength detectors (VWD), enabled the formation of the immiscible IL extraction phase; the insecticides were transferred into the IL phase simultaneously, which enhanced the efficiency and sufficiency, greatly shortening the operation time. The experimental parameters affecting the extraction efficiency including volume of extraction IL, extraction and centrifugation times, volume of the sample solution and exchanging reagent, and addition of organic solvent and salt were investigated and optimized. Under optimized conditions, the extractions yielded recoveries of the target analytes from 82 to 102%. The calibration curves were linear, and the correlation coefficient ranged from 0.9990 to 0.9999 under the concentration levels of 5-200 μg/L. The relative standard deviation (n=6) was 2.9-4.6%. The limits of detection (LODs) for the four insecticides were between 0.98 and 2.54 μg/L.     

New insights on the Cd UPD on Au(111)

The Cd underpotential deposition (UPD) process on Au(111) was analyzed by means of combined electrochemical measurements and in situ scanning tunneling microscopy (STM). In the underpotential range 300?ΔE (mV) ?400, 2D Cd islands are formed on the fcc regions of the Au(111)‐(√3 × 22) reconstructed surface without lifting the reconstruction. At lower underpotentials, the 2D Cd islands grow and, simultaneously, new 2D islands nucleate and coalesce with the previous ones forming a complete condensed Cd monolayer (ML). STM images and long time polarization experiments performed at ΔE = 70 mV demonstrate the formation of an Au? Cd surface alloy. At ΔE = 10 mV, the formation of the complete Cd ML is accompanied by a significant Au? Cd surface alloying and the kinetic results reveal two different solid‐state diffusion processes. The first one, with a diffusion coefficient D₁ = 4 × 10^?17 cm² s^?1, could be ascribed to the mutual diffusion of Au and Cd atoms through a highly distorted (vacancy‐rich) Au? Cd alloy layer. The second and faster diffusion process (D₂ = 7 × 10^?16 cm² s^?1) is associated with the appearance of an additional peak in the anodic stripping curves and could be attributed to the formation of another Cd_zAu_x alloy phase. Copyright © 2008 John Wiley & Sons, Ltd.     

Pt(100)/离子液体OMIPF6界面结构的STM研究

本文运用电化学扫描隧道显微术研究了离子液体OMIPF₆中Pt（100）表面结构在电化学双层区随电极电位的变化. OMI⁺阳离子在Pt（100）表面形成有序吸附结构,并且在约1.2 V宽的电位区间内稳定地存在Pt（100）表面。在电位负于-0.6 V时,有序吸附结构会发生向无序吸附结构的转变. 在电位正于+0.6 V时,较强的静电排斥力才能克服OMIPF₆与Pt（100）表面之间的化学作用,从而导致OMI+阳离子的脱附. 研究表明,OMI+阳离子具有的较长烷基侧链与Pt金属产生的较强化学相互作用是影响该Pt（100）/ OMIPF6界面结构的重要因素.     

Partial stripping of Ag atoms from silver bilayer on a Au(111) surface accompanied with the reductive desorption of hexanethiol SAM

The interfacial structures of Ag bilayer prepared by underpotential deposition on Au(111) (Ag(2ML)/Au(111)) were determined by ex situ scanning tunneling microscopy and in situ surface X-ray scattering measurements before and after oxidative adsorption and after reductive desorption of a self-assembled monolayer (SAM) of hexanethiol (C₆SH) in alkaline ethanol solution. While no structural change was observed after oxidative formation of C₆SH SAM on the Ag(2ML)/Au(111) in an ethanol solution containing 20 mM KOH and 0.1 mM C₆SH, some of the Ag atoms in the bilayer were stripped when the SAM was reductively desorbed. Dedicated to Professor J. O’M. Bockris on the occasion of his 85th birthday.     

In situ STM study of zinc electrodeposition on Au(111) from the ionic liquid 1-ethyl-3-methylimidazolium trifluoromethylsulfonate

The electrodeposition of Zn on Au(111) was investigated with cyclic voltammetry (CV) and in situ scanning tunneling microscopy (STM) in the air and water stable ionic liquid 1-ethyl-3-methylimidazolium trifluoromethylsulfonate ([EMIm]TfO) with a Zn(TfO)₂ concentration of 0.2 M. It has been found that the structure [EMIm]TfO/Au(111) is very complex. Furthermore, the addition of Zn(TfO)₂ changes the interfacial structure significantly. The first STM-probed Zn islands appear at +0.3 V, and their growth leads to the formation of a thin zinc layer. A bulk deposition of Zn is obtained with in situ STM at ?0.1 V. Furthermore, in situ STM reveals that the deposition of Zn is accompanied by the formation of Au-Zn surface alloys.     

An investigation into the activity of the in situ ruthenium(III) chloride catalytic system for the metathesis of 1-octene

A catalytic system consisting of RuCl₃·hydrate, a phosphine and an alkyne were investigated for the metathesis of 1-octene. Hydrogen was used during the reaction to obtain the highest yield of primary metathesis products. The influence of additives (oxygenates) was investigated and the reaction conditions optimized. Metathesis of 1-octene shows the best results at temperatures between 80 and 90 °C if acetic acid or ethanol was used as solvent and a PCy₃/Ru molar ratio of 1. It was also found that both internal and terminal alkynes could be used for the in situ activation of the metathesis precursor during metathesis reactions.     

The interfaces of Au(111) and Au(100) in a hexaalkyl-substituted guanidinium ionic liquid: an electrochemical and in situ STM study

Five hexaalkylguanidinium-based ionic liquids have been synthesised, and based on their cyclic voltammograms the most suited one, N,N-dibutyl-N',N'-diethyl-N',N'-dimethylguanidinium bis(trifluoromethylsulfonyl)imide, has been chosen for electrochemical studies. The surface interaction of this room-temperature ionic liquid with single crystalline gold surfaces (Au(100) and Au(111)) has been investigated using cyclic voltammetry, impedance spectroscopy and in situ scanning tunnelling microscopy (STM). The interfacial capacitance was found to be very low; STM measurements revealed the hex-reconstruction and herringbone reconstruction for Au(100) and for Au(111), respectively, at negative potentials; that is, at these potentials no hints for ad-structures of the cation could be found.     

Preconcentration procedure using in situ solvent formation microextraction in the presence of ionic liquid for cadmium determination in saline samples by flame atomic absorption spectrometry

A simple in situ solvent formation microextraction methodology based on the application of ionic liquid (IL) as an extractant solvent and sodium hexafluorophosphate (NaPF₆) as an ion-pairing agent was proposed for the preconcentration of trace levels of cadmium. In this method cadmium was complexed with O,O-diethyldithiophosphate (DDTP) and extracted into an ionic liquid phase. After phase separation, the enriched analyte in the final solution is determined by flame atomic absorption spectrometry (FAAS). ISFME is a simple and rapid method for extraction and preconcentration of metal ions from sample solutions containing a high concentration of salt. Some effective factors that influence the microextraction efficiency were investigated and optimized. Under the optimum experimental conditions, the limit of detection (3 s) and the enhancement factor were 0.07 μg L⁻¹ and 78, respectively. The relative standard deviation (R.S.D.) was obtained 2.42%. The accuracy of the method was confirmed by analyzing certified reference materials for trace elements in seawater (GBW (E) 080040 seawater). The proposed method was successfully applied for the determination of cadmium in water samples and food grade salts.     

New insights into the Sn underpotential deposition on Au(100)

The underpotential deposition (UPD) of Sn in the system Au(100)/Sn²⁺, SO₄^2? has been studied by classical electrochemical techniques and in situ scanning tunneling microscopy. The results show that the Sn UPD initiates at relatively high potentials with the formation of a quasi‐hexagonal structure characterized as Au(100) ? (√2 × 7)R45°. This expanded overlayer contributes to the modification of the surface morphology which exhibits flat terraces with step edges showing angles of 60 or 120°. At lower potentials two‐dimensional (2D) islands are formed which tend to grow, causing a coverage increase. In the underpotential region close to the formation of the 3D bulk phase the long time polarization experiments indicate the formation of different Au–Sn alloy phases. Copyright © 2011 John Wiley & Sons, Ltd.     

Au+(1S, 3D)与N2O(1Σ+)反应机理的理论研究

采用密度泛函B3LYP方法, O和N用6-311+G*基组, Au+用赝势基组(8s7p6d)/[6s5p3d], 研究了Au+(1S, 3D)离子和N2O(1Σ+)分子的反应机理. 报道了在基态单重态和激发三重态势能面上各反应物、中间体和过渡态的构型特征及能量. 结果表明, 两个主反应通道Au+(1S)+ N2O(1Σ+)→1NA-Complex-1→1NA-TS1→1NA-Complex-2→1NA-Crossing→[3OAuNN]+和Au+(1S)+ N2O(1Σ+)→1NB-Complex→1NB-Crossing→[AuNN(1Σ+)]++O(3P)都需经过反应交叉势能面, 出现“系间窜越”. 用内禀坐标单点计算垂直激发态的方法确定了势能面交叉点, 并用含时密度泛函TD-B3LYP方法进一步探讨了自旋翻转机理.     

Density and surface tension of pure ionic liquid 1-butyl-3-methyl-imidazolium l-lactate and its binary mixture with alcohol and water

The density and surface tension of the pure ionic liquid 1-butyl-3-methyl-imidazolium l-lactate were measured from T (293.15 to 343.15) K. The coefficient of thermal expansion, molecular volume, standard entropy, lattice energy, surface entropy, surface enthalpy, and enthalpy of vaporization were calculated from the experimental values. Density and surface tension were also determined for binary mixtures of {1-butyl-3-methyl-imidazolium l-lactate + water/alcohol (methanol, ethanol, and 1-butanol)} systems over the whole composition range from T (298.15 to 318.15) K at atmospheric pressure. The partial molar volume, excess partial molar volume and apparent molar volume of the component IL and alcohol/water in the binary mixtures were discussed as well as limiting properties at infinite dilution and the thermal expansion coefficients of the four binary mixtures. The surface properties of the four binary mixtures were also discussed.     

A novel gel polymer electrolyte based on poly ionic liquid 1-ethyl 3-(2-methacryloyloxy ethyl) imidazolium iodide

Poly ionic liquid 1-ethyl 3-(2-methacryloyloxy ethyl) imidazolium iodide (PEMEImI) as a single-ion conductor was designed and synthesized. When appropriate amount of suitable plasticizers, I₂ and polyacrylonitrile (PAN) were incorporated into it, the complex formed gel polymer electrolyte. Chemical structure, thermal behavior and ionic conductive properties of the gel polymer electrolyte were investigated by Raman spectra, UV-Vis spectra, differential scanning calorimetry (DSC), and complex impedance analysis, respectively. For the new gel polymer electrolyte, the ionic conductivity of about 1 × 10⁻³ S cm⁻¹ at room temperature was achieved.     

Electro- and acid-catalysis in tetrafluoroborate-based ionic liquid: new alternative routes for the oxidation of sulfides with UHP

By means of anodic activation, BF₄-based ionic liquid was found to play the triple role of electrolysis/reaction medium, supporting electrolyte and pre-catalyst versus the oxidation of sulfides with UHP. Galvanostatic electrolysis in the presence of substrate and UHP molecules allowed the fast, efficient and selective achievement of sulfoxides. Comparable results have been attained by acid catalysis based on R-CSA.     

Ordered arrays of semi-crown ligands on an Au(111) electrode surface: <Emphasis Type="Italic">in situ</Emphasis> STM study

In situ scanning tunneling microscopy (STM) and cyclic voltammetry were employed to investigate the adsorption structures of three semi-crown ligands on an Au(111) surface under the potential control. It is found that all the molecules formed ordered arrays in 0.1 mol/L HClO₄ solution, although their geometric structures are complex and asymmetric. The driving force was supposed to come from the balance between intermolecular and molecule-substrate interactions. High resolution STM images revealed internal molecular structures, orientations and packing arrangements in the ordered adlayers. The results are useful for preparing ordered arrays of transition metal-mediated nanostructures.