Scanning probe microscopy measurements

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]. 

A wide variety of measurements can now be made on single molecules, including electrical (e.g. scanning tunnelling microscopy), magnetic (e.g. spin resonance), force (e.g. atomic force microscopy), optical (e.g. near-field and far-field fluorescence microscopies) and hybrid teclmiques. This contribution addresses only Arose teclmiques tliat are at least partially optical. Single-particle electrical and force measurements are discussed in tire sections on scanning probe microscopies (B1.19) and surface forces apparatus (B1.20). 

The characterization of simple nanostructures is now possible with remarkable detail, but is highly dependent on access to the tools of measurement science and to scanning probe microscopies. 

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. 

Scanning electron microscopy, scanning probe microscopy, ATR-IR spectroscopy, contact angle measurements... 

There are numerous modern developments that have made atomic-scale resolution possible in recent years. In fact, some of these developments in instruments can also be used to measure forces between particles and surfaces. These developments for force measurements are discussed briefly in Section 1.6c and in Vignette 1.8. In this section, we review electron and scanning probe microscopies (SPMs), which allow atomic-scale visualization of surfaces and particles. 

We have seen that electron microscopy and scanning probe microscopies are very complementary techniques to characterize the structure and the morphology of supported clusters. The internal structure can only be resolved by HRTEM while the surface atomic structure can be only revealed by STM or AFM. TEM gives accurate diameter measurements and height can only be measured in profile view that needs special sample preparation. STM or AFM give accurate height measurements but diameters can be obtained only after correction from the tip-sample convolution effect. 

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