Characterization by scanning tunneling microscopy of silver oxydehydrogenation catalysts

A silicon carbide-supported silver catalyst used in the oxydehydrogenation of ethylene glycol to glyoxal has been studied by scanning tunneling microscopy. The surface morphology depends upon reaction conditions. Silver particles normally sinter into large plates covering the support. However, in the presence of diethylphosphite there is a chemical erosion which results in a tortuous and fractal-like surface.     

Electrochemical scanning tunneling microscopy

The electrochemical scanning tunneling microscope was the first tool for the investigation of solid-liquid interfaces that allowed in situ real space imaging of electrode surfaces at the atomic level. Therefore it quickly became an important addition to the repertoire of methods for the determination of the local surface structure as well as the dynamics of reactions and processes taking place at surfaces in an electrolytic environment. In this short overview we present several examples to illustrate the powerful capabilities of the EC-STM, including the observation of clean metal surfaces as well as the adsorption of thin metal layers, specifically adsorbed anions and non-specifically adsorbed organic cations. In several cases the electrode potential has a significant influence on structure and reactivity of the surface that can be explained by the observations made with the EC-STM.     

Fabricating and controlling molecular self-organization at solid surfaces: studies by scanning tunneling microscopy

This account presents a summary of recent work describing the control and fabrication of self-organized molecular adlayers on solid substrates. These results demonstrate that molecules, under appropriate conditions, will self-organize into well-ordered monolayers on various solid surfaces. Using scanning tunneling microscopy (STM) to probe the structure of these molecular architectures, it is possible to determine the surface quality to single molecule resolution. The surface structures can be controlled by external stimuli such as electrode potential and UV-light. The ability to control how these adlayers form is important for constructing surface molecular architectures with useful properties.     

Zirconium oxide supported on Pd(100): Characterization by scanning tunneling microscopy and tunneling spectroscopy

Scanning tunneling microscopy (STM) and tunneling spectroscopy (TS) were used to characterize the structure of a model metal-supported dispersed metal oxide, ZrO₂ on Pd(100). STM images illustrate changes in the surface morphology of the ZrO₂ resulting from various chemical treatments. When the sample was treated in O₂, the ZrO₂ appeared as a smooth, featureless overlayer of varying thickness wetting the Pd. After treatment in H₂, the ZrO₂ formed non-wetting particles on the Pd, with a sharp Pd-ZrO₂ interface. TS provided a fingerprint that verified the presence of a semiconducting overlayer on a metallic support. These results appear to be consistent with X-ray absorption spectra of ZrO₂ supported on Pd black, reported elsewhere.     

Oxygen plasma modification of submicron vapor grown carbon fibers as studied by scanning tunneling microscopy

Scanning tunneling microscopy (STM) has been employed to monitor the changes in surface structure induced by oxygen plasma treatments of submicron vapor grown carbon fibers (VGCFs). It is shown that the fibers preserve their general smoothness upon plasma oxidation and that the structural changes brought about by this treatment essentially take place only at the atomic scale, where the relatively ordered domains typical of the untreated material are replaced by atomically rough and disordered structures. These atomic-scale changes imply the modification of some physico-chemical properties of the fiber surface, such as concentration of oxygen functionalities. The STM results, together with those obtained from nitrogen physical adsorption measurements, suggest that the potential improvement of plasma treatment in VGCF-matrix adhesion for application in composite materials should proceed mainly from chemical bonding due to the addition of functional groups rather than from increased mechanical interlocking.     

Easily made and handled carbon nanocones for scanning tunneling microscopy and electroanalysis

Well-formed carbon nanocones at the ends of micrometer-diameter carbon fibers (CFs) were fashioned into functional tips for scanning tunneling microscopy (STM) and miniaturized voltammetric sensors. Sharpening of single graphite filaments was achieved by simple DC electrochemical etching in 0.1 N NaOH. Operated as STM tips, pointed CFs resolved in air the contour and surface morphology of a nanoscopic Au line pattern and imaged in vacuum a Si (1 1 1) surface with clear atomic resolution. Subjecting already etched CFs to tip-sparing insulation with electrodeposited paint produced conical carbon ultramicroelectrodes (UMEs) with effective radii down to about 900 nm. Comparative cyclic voltammetry trials in alkaline, neutral and acidic solutions showed that the conical carbon UME’s had a wider practical potential window for electroanalytic applications than, for instance, Pt disk UMEs. The CF-based conical sensors described here are exceptionally easy to make with simple laboratory equipment and perform well in STM topography imaging and voltammetry. The inherent simplicity of sensor production widens the field of potential users, and offers clear advantages over existing types of UMEs, in particular those based on carbon nanotubes, which are especially hard to handle in an optical microscope setting.     

Vibration-assisted upconversion of molecular luminescence induced by scanning tunneling microscopy

We investigate the effects of coupling between a molecular exciton, which consists of an electron and a hole in a molecule, and a surface plasmon (exciton-plasmon coupling) on the electron transitions of the molecule using nonequilibrium Green’s function method. Due to the exciton-plasmon coupling, excitation channels of the molecule arise in the energy range lower than the electronic excitation energy of the molecule. It is found that the electron transitions via these excitation channels give rise to the molecular luminescence and the vibrational excitations at the bias voltage lower than the electronic excitation energy of the molecule. Our results also indicate that the vibrational excitations assist the emission of photons, whose energy exceeds the product of the elementary charge and the bias voltage, (upconverted luminescence).     

Periodic, pearl chain-like nanostructure observed by scanning tunneling microscopy

A periodic, pearl chain-like nanostructure is observed in ultrahigh vacuum scanning tunneling microscopy (UHV-STM) of chromium filled carbon nanotubes. The structure displays one dimensional periodic morphology, with periodicity of ∼3.3 nm. Atomically resolved STM image of the pearl chain structure shows hexagonal periodicity. The origin of the pearl chain structure is discussed.     

Probing the morphology of polypropylene fibres by scanning probe microscopy

This paper highlights the application of scanning probe microscopy, notably atomic force microscopy in contact mode supported by lateral force microscopy, to the investigation of changes in the morphology of polypropylene (PP) monofilaments during melt-extrusion and subsequent drawing. A gradual deformation at the fibre surface from a spherulitic structure to a shish-kebab type structure is observed for the gravity spun and as-spun variants. In the drawn PP filaments, the surface structure is predominantly fibrillar in character, though the nature of the fibrillar structure is influenced by the drawing conditions. Wide angle X-ray scattering analysis, in conjunction with SPM, indicates contrasting features of surface and bulk crystal structure both at the as-spun and drawn stages of production. In addition, an unusual WAXS diffraction pattern is observed for the cold drawn PP filament. Studies of the bulk structures of the fibres by investigating fibre cross-sections using SPM will be the subject of a companion paper.     

Using scanning tunneling microscopy to characterize adsorbates and reactive intermediates on transition metal oxide surfaces

Scanning tunneling microscopy (STM) is demonstrated to be a powerful tool to characterize adsorption and reaction on oxide surfaces by imaging molecular adsorbates and reactive intermediates. The molecules were used to probe surface structure and to study surface reactivity spatially at the atomic level. Results for three systems are presented: alcohol adsorption on WO₃(0 0 1), carboxylates on the anatase polymorph of TiO₂, and propene adsorption on a PdO monolayer on Pd(1 0 0). When the alcohols were exposed to the WO₃(0 0 1)-c(2×2) surface at room temperature the molecules could not be imaged. Heating the surface to temperatures above a water desorption peak associated with alcohol deprotonation, however, allowed 1-propoxide to be imaged. The images reveal that the alkoxide has no preference for defects, rather it binds to W⁶⁺ ions exposed on the fully oxidized c(2×2) surface. Temperature-programmed desorption revealed that alkoxides at these sites undergo only dehydration reactions. To probe the structure of the unusual (1×4) reconstruction on anatase (0 0 1), formic and acetic acid adsorption were used. Following dissociative adsorption, both formate and acetate adsorb solely centered atop the bright rows that define the surface reconstruction, and the molecules are always at least two lattice constants apart. This result may be attributed to carboxylates bridge-bonded to Ti atoms at the center of the bright rows. This finding eliminates several suggested models of the reconstruction and suggests that a recently proposed ad-molecule model is a good representation of the surface structure. Propene was observed to initially randomly adsorb on the PdO monolayer. At higher coverages, however, the adsorbates cluster, disrupting the surface structure and causing the adsorption rate adjacent to the clusters to increase. Temperature-programmed reaction revealed that once propene adsorbs, the oxide monolayer catalyzes its oxidation at lower temperatures than metallic Pd, but that the propene sticking coefficient on the ordered oxide layer is a factor of 5 lower.     

Direct observations of changes in surface structures by scanning tunneling microscopy

Recently, we have studied the interaction of reactive adsorbates H, C, O, and S with Ni and Cu surfaces by scanning tunneling microscopy (STM). In this paper, we briefly illustrate and discuss how such studies provide significant insight into the understanding of dynamic surface processes such as adsorbate-induced restructuring, surface reactions, and adsorbate-adsorbate interactions. The STM results demonstrate that there is a strong coupling between the chemisorption/reaction process and the distortion of the metal surface.     

Characterization of modified polypropylene by scanning electron microscopy

Characterizing the morphology of modified multiphasic polymer systems, as are often applied for improving the impact strength, is normally a complicated and tedious task. Nevertheless, knowledge about the volume fraction and particle‐size distribution of the elastomer phase is important for the specific development of high‐impact systems. Direct production in the reactor enables only indirect control of these two quantities. Computer‐controlled scanning electron microscopy in combination with image processing allows an automated measurement of both all the necessary particle parameters (size distribution, shape, orientation, etc.) and the elastomer content of the material. Since bulk materials are used for the investigation, additionally, three‐dimensional information about the structure of the material can be gained by simply varying the electron energy, without the necessity to resort to multiple slices. This information is especially important in the case of particles with extremely irregular shapes, as obtained, for example, by strong agglomeration of the modifier particles. The mathematical routines used for calculation of the particle‐size distributions from the measured profile‐size distributions cannot be applied in such cases. The method was tested for several materials with significantly different compositions, both immediately after molding and also after a subsequent thermal relaxation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1152–1161, 2000     

Spin-polarized scanning tunneling microscopy: breakthroughs and highlights

The principle of scanning tunneling microscopy, an imaging method with atomic resolution capability invented by Binnig and Rohrer in 1982, can be adapted for surface magnetism studies by using magnetic probe tips. The contrast mechanism of this so-called spin-polarized scanning tunneling microscopy, or SP-STM, relies on the tunneling magneto-resistance effect, i.e. the tip-sample distance as well as the differential conductance depend on the relative magnetic orientation of tip and sample. To illustrate the working principle and the unique capabilities of SP-STM, this compilation presents some key experiments which have been performed on various magnetic surfaces, such as the topological antiferromagnet Cr(001), a double-layer of Fe which exhibits a stripe- domain pattern with about 50 nm periodicity, and the Mn monolayer on W(110), where the combination of experiment and theory reveal an antiferromagnetic spin cycloid. Recent experimental results also demonstrate the suitability of SP-STM for studies of dynamic properties, such as the spin relaxation time of single magnetic nanostructures.     

Investigation of diamond etching and growth by in situ scanning tunneling microscopy

Recently we published a new experimental set-up for the investigation of dynamic processes under diamond deposition conditions. In the present paper the first measurements of diamond etching and growth with this set-up are presented. Etching experiments at 500°C substrate temperature reveal no etching of the pre-grown diamond film used as sample, whereas at 530°C rapid etching of a (111)-faceted crystal and slow etching of a (100)-faceted crystal is visible. Similar, at 500°C no growth could be detected on a boron doped (100)-single crystal, but at 530°C growth was monitored with a rate comparable with that of the etching rate of the (100)-plane at the same substrate temperature (about 10 nm h⁻¹).     

Imaging the structure and porosity of active carbons by scanning tunneling microscopy

Scanning tunneling microscopy (STM) has been employed for a comparative structural characterization, down to the atomic scale, of a representative set of porous carbons with different adsorption characteristics and prepared either by activation (physical or chemical) or templating techniques. The studied materials included a chemically activated, supermicroporous high surface area carbon, two activated carbons containing both micro- and mesopores synthesized by physical activation, an ultramicroporous carbon molecular sieve, and an ordered microporous carbon templated in the nanochannels of zeolite Y. In general, good agreement was found between the porous structures as imaged by STM and the porous texture derived from gas adsorption data for all the carbons investigated. The activated carbon samples were dominated by networks of slit type micropores and, in some cases, by mesopores of varied morphologies. By contrast, the zeolite-templated carbon exhibited rounded micropore morphology, and the carbon molecular sieve displayed a rather featureless conformation dominated by voids only below 1 nm wide. The structural differences observed by STM were interpreted in terms of the different preparation procedures of the studied carbons. In particular, the templated carbon consisted of minute clusters about 1 nm in diameter that were interpreted to be formed within the extremely confined, microporous spaces of the zeolite Y template.     

Strong interaction between graphene edge and metal revealed by scanning tunneling microscopy

The interaction between a graphene edge and the underlying metal is investigated through the use of scanning tunneling microscopy (STM) and density functional theory (DFT) calculations and found to influence the geometrical structure of the graphene edge and its electronic properties. STM study reveals that graphene nanoislands grow on a Pt(1 1 1) surface with the considerable bending of the graphene at the edge arising from the strong graphene-edge–Pt-substrate interactions. Periodic ripples along the graphene edge due to both the strong interaction and the lattice mismatch with the underlying metal were seen. DFT calculations confirm such significant bending and also reproduce the periodic ripples along the graphene edge. The highly distorted edge geometry causes strain-induced pseudo-magnetic fields, which are manifested as Landau levels in the scanning tunneling spectroscopy. The electronic properties of the graphene edge are thus concluded to be strongly influenced by the curvature rather than the localized states along the zigzag edge as was previously predicted.     

Characterization of foulant removal by confocal scanning laser microscopy

A review of past marketing-related research in the area of recycled water has been conducted. Findings are reported within the main areas of past research: willingness to adopt different forms of usage of recycled water, concerns of the general public towards the use of recycled water, the socio-demographic profile of early adopters, strategies to increase acceptance and adoption of recycled water in communities, perceived benefits among users of recycled water. The limitations of prior studies are reviewed and gaps identified, leading to recommendations for a future marketing-related research agenda to support public acceptance of recycled water in communities.     

Reduction potentials of heteropolyacid catalysts probed by scanning tunneling microscopy and UV-visible spectroscopy

Reduction potentials of heteropolyacid (HPA) catalysts were probed by scanning tunneling microscopy (STM) and UV-visible spectroscopy. Correlations between reduction potentials and NDR (negative differential resistance) peak voltages, and between reduction potentials and absorption edge energies of HPA catalysts were established. The reduction potentials of HPA catalysts have been shown to follow similar trends to the NDR peak voltages of selfassembled HPA monolayers and the absorption edge energies of bulk HPAs. In the UV-visible spectra of HPA catalysts, lower absorption edge energies corresponded to higher reduction potentials of the HPAs.     

Monitoring surfaces on the molecular level during catalytic reactions at high pressure by sum frequency generation vibrational spectroscopy and scanning tunneling microscopy

Sum frequency generation (SFG), using non-linear laser optics, detects vibrational spectra of submonolayer amounts of adsorbates with excellent energy and time resolution. Scanning tunneling spectroscopy (STM) is sensitive to the atomic surface structure; readily imaging defects, steps and kinks as well as stationary adsorbed species. Both of these techniques can be used during reactions at high pressures and temperatures to obtain molecular information in situ. We report studies of propylene hydrogenation over Pt(111) crystal surfaces at atmospheric pressures and 300 K using SFG and STM. Four surface species (2-propyl, -bonded propylene, di -bonded propylene, and propylidyne) were identified; the first two being implicated as reaction intermediates. The platinum surface structure remains unchanged during the reaction, consistent with the structure insensitive nature of olefin hydrogénation. Propylene decomposition induced substantial surface reconstruction.