Electrochemical scanning probe microscopy

Facci, P., Alliata, D., and Cannistraro, S. (2001) Potential-induced resonant tunneling through a redox metalloprotein investigated by electrochemical scanning probe microscopy. Ultramicroscopy, 89,... 

Davis, J.J., Hill, H.A.O., and Bond, A.M. (2000) The application of electrochemical scanning probe microscopy to the interpretation of metalloprotein voltammetry. 

An electrochemical scanning probe microscopy and Raman spectroscopy investigation of thin CdS films grown by electrochemical atomic layer epitaxy (ECALE) aimed at understanding the role played by the order of deposihon on film quality were reported [161]. 

The growth and the surface properties of polypyrrole on single crystal graphite electrodes as studied by in-situ electrochemical scanning probe microscopy... 

Scanning electrochemical cell microscopy (SECCM) is a recent innovation [161, 167] in electrochemical scanning probe microscopy [168] that has been proven particularly powerful for visualizing electroactivity. In the case of HOPG, the SECCM response also informs on the location of the measurement, that is, basal... 

The development of scanning probe microscopies and x-ray reflectivity (see Chapter VIII) has allowed molecular-level characterization of the structure of the electrode surface after electrochemical reactions [145]. In particular, the important role of adsorbates in determining the state of an electrode surface is illustrated by scanning tunneling microscopic (STM) images of gold (III) surfaces in the presence and absence of chloride ions [153]. Electrodeposition of one metal on another can also be measured via x-ray diffraction [154]. 

Gewirth A A and Niece B K 1997 Electrochemical applications of in situ scanning probe microscopy Chem. Rev. 971129... 

As mentioned above, the methods based on detection of electrons or ions or probing the electrode surface by these particles are generally handicapped by the necessity to move the studied electrode into vacuum, i.e. to work ex-situ. There are, however, two important exceptions to this rule electrochemical mass spectrometry and electrochemical scanning tunnelling microscopy. 

It is noteworthy that prior to the advent of scanning probe microscopy electrochemically driven reconstruction phenomena had been identified and studied using traditional macroscopic electrochemical measurements [210,211], However, STM studies have provided insight as to the various atomistic processes involved in the phase transition between the reconstructed and unreconstructed state and promise to provide an understanding of the macroscopically observed kinetics. An excellent example is provided by the structural evolution of the Au(lOO) surface as a function of potential and sample history [210,211,216-223], Flame annealing of a freshly elec-tropolished surface results in the thermally induced formation of a dense hexagonal close-packed reconstructed phase referred to as Au(100)-(hex). For carefully annealed crystals a single domain of the reconstructed phase... 

Scanned probe microscopies (SPM) that are capable of measuring either current or electrical potential are promising for in situ characterization of nanoscale energy storage cells. Mass transfer, electrical conductivity, and the electrochemical activity of anode and cathode materials can be directly quantified by these techniques. Two examples of this class of SPM are scanning electrochemical microscopy (SECM) and current-sensing atomic force microscopy (CAFM), both of which are commercially available. 

Pb UPD on Ag(lll) and Ag(lOO) has been studied using X-ray diffraction method, electrochemical impedance spectroscopy, and in situ scanning probe microscopy [272, 286-288]. This process has been reviewed in [265, 270], see Table 2. Both structure and voltammetric behavior are dependent on the Ag(h, k, 1) plane [265, 289]. 

Figure 22. The tunneling current, I, measured between two metal electrodes (tungsten en platinum) separated by a vacuum barrier as a function of the difference in electrochemical potential (here denoted as C/emitter-anode) the distance between the two electrodes (12, 20, 17 A) is indicated in the figure. Reprinted from Scanning Probe Microscopy and Spectroscopy , R. Wiesendanger, Cambridge University Press 1994...

Probes that are most sensitive to defects [scanning probe microscopy (e.g., AFM and STM) and electrochemistry] are difficult to apply to the multilayered LB systems used for electron-transfer experiments. AFM studies are not sensitive to buried defects, and the insulating nature of the films complicates STM studies. These systems typically are unstable under conditions necessary to probe them electrochemically. 

Chapter 4, by Batzill and his coworkers, describes modern surface characterization techniques that include photoelectron diffraction and ion scattering as well as scanning probe microscopies. The chapter by Hayden discusses model hydrogen fuel cell electrocatalysts, and the chapter by Ertl and Schuster addresses the electrochemical nano structuring of surfaces. Henry discusses adsorption and reactions on supported model catalysts, and Goodman and Santra describe size-dependent electronic structure and catalytic properties of metal clusters supported on ultra-thin oxide films. In Chapter 9, Markovic and his coworkers discuss modern physical and electrochemical characterization of bimetallic nanoparticle electrocatalysts. 

Single-crystal, atomically planar electrode surfaces have paved the way for introducing the scanning probe microscopies of STM and AFM in the bioelectrochemical sciences. The powerful in situ STM technology has increased the structural resolution of (bio)electrochemical electrode surfaces to the molecular and... 

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