Imaging sequential dehydrogenation of methanol on Cu(110) with a scanning tunneling microscope

Adsorption of methanol and its dehydrogenation on Cu(110) were studied by using a scanning tunneling microscope (STM). Upon adsorption at 12 K, methanol preferentially forms clusters on the surface. The STM could induce dehydrogenation of methanol sequentially to methoxy and formaldehyde. This enabled us to study the binding structures of these products in a single-molecule limit. Methoxy was imaged as a pair of protrusion and depression along the [001] direction. This feature is fully consistent with the previous result that it adsorbs on the short-bridge site with the C-O axis tilted along the [001] direction. The axis was induced to flip back and forth by vibrational excitations with the STM. Two configurations were observed for formaldehyde, whose structures were proposed based on their characteristic images and motions.     

Imaging and vibrational spectroscopy of single pyridine molecules on Ag(110) using a low-temperature scanning tunneling microscope

A scanning tunneling microscope (STM) was used to extract the images of single, isolated pyridine molecules adsorbed on Ag(110) and to record their vibrational spectrum at 13 K. On the STM image, the pyridine molecule appears as an elongated protrusion along the [001] direction on top of a silver atom, indicating that it is bonded through its nitrogen lone pair electrons. STM inelastic electron tunneling spectroscopy of the adsorbed pyridine revealed C-D and C-H stretch modes at 282 and 378 meV, respectively.     

In situ scanning tunneling microscopy investigation of sulfur oxidative underpotential deposition on Ag(100) and Ag(110)

Underpotential (UPD) deposition of sulfur from Na(2)S solution in 0.1 M NaOH was studied on Ag(100) and Ag(110) using in situ scanning tunneling microscopy (STM). The cyclic voltammogram on Ag(100) presents two broad peaks, whereas three partial overlapping peaks and a sharper one are observed on Ag(110). STM measurements carried out during the whole UPD process show that progressively more compact structures are formed as the applied potential is scanned toward more positive potentials. More precisely, p(2×2), c(2×6), and c(2×2) were found on Ag(100) at E = -1.25, -1.0, and -0.9 V, respectively. Less definite conclusions can be drawn for the structures of S overlayers on Ag(110). However, the experimental findings are consistent with an incomplete p(2×1) at potentials preceding the sharp peak, and with a c(2×2) structure at E = -0.9 V vs Ag/AgCl, KCl(sat). The coverage values calculated on the basis of the hypothesized structures have been compared with the values obtained from chronocoulometric measurements at the most positive potentials investigated. Thus, the experimental coverage θ = 0.5 coincides with the coverage calculated for the c(2×2) structure found on Ag(110) at E = -0.9 V by STM, whereas the experimental coverage θ = 0.42 suggests that a mixture of structures c(2×6) and c(2×2) is formed on Ag(100).     

In situ observation of CO oxidation on Ag110(2 x 1)-O by scanning tunneling microscopy: structural fluctuation and catalytic activity

On the added-row reconstructed Ag(110)(nx1)-O surfaces where one-dimensional -Ag-O-Ag-O- chains arrange periodically, the clean-off reaction of O adatoms by CO was investigated using variable temperature scanning tunneling microscopy (VT-STM). Based on the in situ STM observations of the surface structure variation in the course of the reaction at various temperatures, we found that the reaction kinetics are significantly affected by the structural transition of AgO chains from a solid straight line configuration to dynamically fluctuating configurations. Below 230 K where the chains are straight, the reaction takes place only at the end of the chains, so that the reaction progresses in the zero-order kinetics with the reaction front propagating along the chain. The temperature dependence of the reaction rates yields the activation barrier of 41 kJ/mol and the preexponential factor of 1.7 x 10(3) cm(-2) s(-1). At room temperature, the reaction rate is drastically accelerated when almost half of the O adatoms are eliminated and the chains start fluctuating. The dynamic formation of active sites equivalent to the end of chains upon the chain fluctuation results in the nonlinear increase of the reaction rate.     

Oxygen vacancy promoting catalytic dehydration of formic acid on TiO2(110) by in situ scanning tunneling microscopic observation

The catalytic dehydration reaction processes of formic acid on a TiO2(110) surface at 350 K have been studied to visualize reaction intermediates and their dynamic behaviors by scanning tunneling microscopy. Three types of configurations of adsorbed formates on the surface were identified by their shapes and positions in STM images. Successive STM observations revealed transformations among the three configurations, i.e., bridge formate on a 5-fold coordinated Ti4+ row, bridge formate on an oxygen vacancy site with an oxygen atom of formate and on a 5-fold coordinated Ti4+ ion and with the other formate oxygen atom, and a monodentate formate on an oxygen vacancy site with an oxygen atom of formate. The decomposition of the monodentate formate to carbon monoxide and hydroxyl was also imaged, which is a rate-determining step in the catalytic dehydration of formic acid. Combined with first-principle DFT calculations, the overall reaction processes of the catalytic dehydration of formic acid on the surface have been elucidated. Oxygen vacancies on the surface that can be produced by dehydration of two hydroxyls in situ under the catalytic reaction conditions are essential for the reaction.     

Manipulation and characterization of xenon-metalloporphyrin complexation with a scanning tunneling microscope

The formation of a series of Xe-CuEtioI [Cu(II) etioporphyrin I] complexes on Cu(001) surface was identified by scanning tunneling microscopy (STM) at cryogenic condition. The binding sites of xenon to CuEtioI molecule were directly revealed by high-resolution STM images in combination with controlled manipulation. The interaction between xenon atoms and CuEtioI in the on-top configuration is suggestive of a charge-induced dipole interaction. The structural parameters obtained with the STM complement results from spectroscopic studies of van der Waals complexes.     

Direct observation of polymer-stabilized blue phase I structure with confocal laser scanning microscope

The three-dimensional structure of polymer-stabilized blue phase with the order of optical wavelength was nondestructively investigated by a confocal laser scanning microscope. The periodical patterns corresponding to the bcc lattice were observed not only on the surface but also in the internal region. The visualization mechanism was expected to be back scattering caused by liquid crystal order.     

Characterization of mo deposited on a TiO2(110) surface by scanning tunneling microscopy and Auger electron spectroscopy

The properties of Mo ultrathin films deposited on a TiO2(110) surface were investigated by scanning tunneling microscopy (STM) and spectroscopy (STS), as well as by Auger electron spectroscopy (AES). The substrate exhibited mainly large (1 x 1) terraces decorated by additional [001] rows (missing or added 1D structures) of reduced TiO(x) phases. Only a few percent of the surface exhibited a cross-linked (1 x 2) arrangement. The deposition of Mo layers at room temperature with a rate of approximately 0.4 monolayer/ min resulted in nanoclusters of 1-2 nm with a low-profile shape (2D-like). Preferential decoration of the atomic steps was not found; at the same time, the 1D defect sites of missing or added rows on the (110) terraces were characteristically decorated by larger Mo nanocrystallites. This behavior indicates that the mobility of Mo atoms is higher on the more reduced regions of the substrate. The high dispersion of the Mo adlayer changed only slightly on annealing up to 700 K; in the range of 900-1050 K, however, a significant increase of the particle size accompanied by splitting of the TiO2(110) terraces was observed. This behavior may be explained by the partial oxidation of the supported Mo (accompanied by the reduction of the substrate) into tetragonal crystallites oriented and slightly elongated in the [001] or [110] direction of the TiO2(110) support. STS measurements indicated that the crystallites or the support/crystallite interface formed above 900 K possesses a wide band gap. The annealing above 1050 K resulted in the disappearance of Mo from the TiO2(110) surface, which may be explained by the formation and sublimation of MoO3 species at the perimeter of the nanoparticles. The change of AES signal intensities for O(KLL) and Mo(MNN) as a function of the annealing temperature also supports this mechanism.     

Direct observation and control of hydrogen-bond dynamics using low-temperature scanning tunneling microscopy

Hydrogen(H)-bond dynamics are involved in many elementary processes in chemistry and biology. Because of its fundamental importance, a variety of experimental and theoretical approaches have been employed to study the dynamics in gas, liquid, solid phases, and their interfaces. This review describes the recent progress of direct observation and control of H-bond dynamics in several model systems on a metal surface by using low-temperature scanning tunneling microscopy (STM). General aspects of H-bond dynamics and the experimental methods are briefly described in chapter 1 and 2. In the subsequent four chapters, I present direct observation of an H-bond exchange reaction within a single water dimer (chapter 3), a symmetric H bond (chapter 4) and H-atom relay reactions (chapter 5) within water–hydroxyl complexes, and an intramolecular H-atom transfer reaction (tautomerization) within a single porphycene molecule (chapter 6). These results provide novel microscopic insights into H-bond dynamics at the single-molecule level, and highlight significant impact on the process from quantum effects, namely tunneling and zero-point vibration, resulting from the small mass of H atom. Additionally, local environmental effect on H-bond dynamics is also examined by using atom/molecule manipulation with the STM.     

Adsorbed states and scanning tunneling microscopy induced migration of acetylene on Cu(110)

The authors have studied adsorption of acetylene on Cu(110) by means of low-temperature scanning tunneling microscopy. Adsorbed molecules preferentially aggregate at 40 K to yield dimer, trimer, and larger islands on the surface. Isolated species (monomer) adsorbs on the fourfold hollow site with approximately sp3 rehybridization as characterized by inelastic electron tunneling spectroscopy. Tunneling electron induces an acetylene molecule to migrate along the trough of Cu(110). The migration proceeds in two steps: the molecule first hops to the adjacent long-bridge site and then to the next fourfold site. The voltage and current dependencies of the hopping probability show that the migration is induced by inelastic electron tunneling that causes vibrational excitation of mainly C-H stretch mode.     

Luminescence from 3,4,9,10-perylenetetracarboxylic dianhydride on Ag(111) surface excited by tunneling electrons in scanning tunneling microscopy

The electronic excitations induced with tunneling electrons into adlayers of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) on Ag(111) have been investigated by in situ fluorescence spectroscopy in scanning tunneling microscopy (STM). A minute area of the surface is excited by an electron tunneling process in STM. Fluorescence spectra strongly depend on the coverage of PTCDA on Ag(111). The adsorption of the first PTCDA layer quenches the intrinsic surface plasmon originated from the clean Ag(111). When the second layer is formed, fluorescence spectra are dominated by the signals from PTCDA, which are interpreted as the radiative decay from the manifold of first singlet excited state (S(1)) of adsorbed PTCDA. The fluorescence of PTCDA is independent of the bias polarity. In addition, the fluorescence excitation spectrum agrees with that by optical excitation. Both results indicate that S(1) is directly excited by the inelastic impact scattering of electrons tunneling within the PTCDA adlayer.     

Probe microscope observation of platinum atoms deposited on the TiO2(110)-(1 x 1) surface

Titanium dioxide (TiO2) (110) surfaces with Pt adatoms were examined using a noncontact atomic force microscope (NC-AFM) and a Kelvin probe force microscope (KPFM). Topographic images with NC-AFM identify Pt atoms adsorbed at three different sites. These sites are on the Ti atom rows, on the O atom rows, and in O atom vacancies. Most Pt adatoms were observed on Ti atom rows. Successively recorded images show that the Pt adatoms on Ti atom rows (adatoms A) and O atom rows (adatoms C) are mobile while the adatoms in the O atom vacancies (adatoms B) are not. Adatoms A and adatoms B were identified in KPFM images. However, adatoms C were not visualized in KPFM images because they moved quickly or were swept out by the tip. The KPFM measurements reveal that the work function on adatoms A are lower than that on the surrounding (1 x 1) surface by 0.24 eV whereas adatoms B reduced the work function by 0.26 eV. The work function decrease is interpreted with an electric dipole moment directed toward the vacuum, as a result of electron transfer from the adatoms to the TiO2 substrate. In an O atom vacancy, the adatom B is in contact with two Ti atoms and therefore the electron transfer can be enhanced.     

The initiation and characterization of single bimolecular reactions with a scanning tunneling microscope

A scanning tunneling microscope (STM) operating at 9 K in ultrahigh vacuum was used to initiate a bimolecular reaction between isolated hydrogen sulfide and dicarbon molecules on the Cu(001) surface. The reaction products ethynyl (CCH) and sulfhydryl (SH) were identified by inelastic electron tunneling spectroscopy (STM-IETS) and by sequentially removing hydrogen atoms from an H2S molecule using energetic tunneling electrons. For comparison, the thermal diffusion and reaction of H2S and CC at 45 K and H2O and CC at 9 K were also observed.     

Pyridine adsorption on Ag(110)

The adsorption of pyridine on a clean Ag(110) surface was characterized with ultraviolet photoemission spectroscopy, flash desorption and Auger electron spectroscopy. Pyridine condenses on the silver surface below 190 K and rapidly forms multiple layers. At temperatures above 235 K pyridine is present in submonolayer concentrations. At 275 K pyridine is chemisorbed on Ag(110).     

Potential distribution in the solution interface of a scanning tunneling microscope

The linearized Poisson—Boltzmann equation is solved in the region between a sphere and a plane, which is modelling the electrolyte solution interface between the tip and the substrate in a scanning tunneling microscope. A series expansion in modified Bessel functions and Legendre polynomials, which are solutions to the linearized Poisson—Boltzmann equation, is used to fit the boundary conditions. Another numerical method of finite difference is also used with the domain transformed into bispherical coordinates. Results for cases of different potential values on the boundary surfaces and different distances of the sphere from the plane are presented.     

Nanoscale coupling of photons to vibrational excitation of Ag nanoparticle 2D array studied by scanning tunneling microscope light emission spectroscopy

Scanning tunneling microscope light emission (STM-LE) spectroscopy has been utilized to elucidate the luminescence phenomena of Ag nanoparticles capped with myristate (myristate-capped AgNP) and 2-methyl-1-propanethiolate (C(4)S-capped AgNP) on the dodecanethiol-precovered Au substrate. The STM imaging revealed that myristate-capped AgNPs form an ordered hexagonal array whereas C(4)S-capped AgNPs show imperfect ordering, indicating that a shorter alkyl chain of C(4)S-capped AgNP is not sufficient to form rigid interdigitation. It should be noted that such a nanoparticle ordering affects the luminescence properties of the Ag nanoparticle. We found that the STM-LE is only detected from the Ag nanoparticles forming the two-dimensional superlattice. This indicates that the STM-LE of the Ag nanoparticle is radiated via the collective excitation of the local surface plasmon resonance (LSPR) spread over the Ag nanoparticles. Note that the STM-LE spectra of the Ag nanoparticles exhibit spike-like peaks superimposed on the broad light emission peak. Using Raman spectroscopy, we concluded that the spike-like structure appearing in the STM-LE spectra is associated with the vibrational excitation of the molecule embedded between Ag nanoparticles.     

Unisized two-dimensional platinum clusters on silicon(111)-7x7 surface observed with scanning tunneling microscope

Uni-sized platinum clusters (size range of 5-40) on a silicon(111)-7 x 7 surface were prepared by depositing size-selected platinum cluster ions on the silicon surface at the collision energy of 1.5 eV per atom at room temperature. The surface thus prepared was observed by means of a scanning tunneling microscope (STM) at the temperature of 77 K under an ambient pressure less than 5 x 10(-9) Pa. The STM images observed at different cluster sizes revealed that (1) the clusters are flattened and stuck to the surface with a chemical-bond akin to platinum silicide, (2) every platinum atom occupies preferentially the most reactive sites distributed within a diameter of approximately 2 nm on the silicon surface at a cluster size up to 20, and above this size, the diameter of the cluster increases with the size, and (3) the sticking probability of an incoming cluster ion on the surface increases with the cluster size and reaches nearly unity at a size larger than 20.     

HCOO在Cu(110)、Ag(110)和Au(110)表面的吸附

采用密度泛函理论(DFT)以及广义梯度近似方法(GGA)计算了甲酸根(HCOO)在Cu(110)、Ag(110)和Au(110)表面的吸附. 计算结果表明, 短桥位是最稳定的吸附位置, 计算的几何参数与以前的实验和计算结果吻合. 吸附热顺序为Cu(110)(-116 kJ·mol-1)>Ag(110)(-57 kJ·mol-1)>Au(110)(-27 kJ·mol-1), 与实验上甲酸根的分解温度相一致. 电子态密度分析表明, 吸附热顺序可以用吸附分子与金属d-带之间的Pauli 排斥来关联, 即排斥作用越大, 吸附越弱. 另外还从计算的吸附热数据以及实验上HCOO的分解温度估算了反应CO2+1/2H2→HCOO的活化能, 其大小顺序为Au(110)>Ag(110)>Cu(110).