Scanning SECM

SECM Scanning electrochemical microscopy [40] An STM serves as microelectrode to reduce electroactive species Electrochemical reactions on surfaces... 

The radius and shape of the solution meniscus and the thickness of the glass wall can also be evaluated from SECM measurements, in which a pipette can be used as a scanning microprobe (see Section IV.D). 

Alternatively, a higher rate of mass transport in steady-state measurements with a larger UME can be obtained by using it as a tip in the scanning electrochemical microscope (SECM). The SECM has typically been employed for probing interfacial ET reactions [29]. Recently, micropipettes have been used as SECM probes (see Section IV.B below) [8b,30]. Although the possibility of probing simple and assisted IT at ITIES by this technique was demonstrated, no actual kinetic measurements have yet been reported. 

In scanning electrochemical microscopy (SECM) a microelectrode probe (tip) is used to examine solid-liquid and liquid-liquid interfaces. SECM can provide information about the chemical nature, reactivity, and topography of phase boundaries. The earlier SECM experiments employed microdisk metal electrodes as amperometric probes [29]. This limited the applicability of the SECM to studies of processes involving electroactive (i.e., either oxidizable or reducible) species. One can apply SECM to studies of processes involving electroinactive species by using potentiometric tips [36]. However, potentio-metric tips are suitable only for collection mode measurements, whereas the amperometric feedback mode has been used for most quantitative SECM applications. 

Perhaps the most important experimental progress made recently in electrochemistry was the introduction of a scanning electrochemical microscope (SECM). Tsionsky et al. have used SECM to study also the rate of ET across a lipid monolayer at the water-benzene interface [48,49]. The presence of the monolayer decreased the rate of ET, being the decrease more significant for longer hydrocarbon chains and larger lipid concentration in solution. It was thus concluded that the ET reaction does not occur at defect sites in the lipid monolayer. 

UMEs decrease the effects of non-Earadaic currents and of the iR drop. At usual timescales, diffusional transport becomes stationary after short settling times, and the enhanced mass transport leads to a decrease of reaction effects. On the other hand, in voltammetry very high scan rates (i up to 10 Vs ) become accessible, which is important for the study of very fast chemical steps. For organic reactions, minimization of the iR drop is of practical value and highly nonpolar solvents (e.g. benzene or hexane [8]) have been used with low or vanishing concentrations of supporting electrolyte. In scanning electrochemical microscopy (SECM [70]), the small size of UMEs is exploited to locahze electrode processes in the gm scale. 

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. 

A complementary microscopy to SECM is CAFM, in which the AFM tip is made of a metal such that current can be measured as the tip is scanned, in contact, across the surface. s Conducting-AFM offers the advantage of directly measuring local electrical... 

The preparation and application of SAM systems patterned by STM and their use in catalysis was demonstrated by Wittstock and Schuhmann [123]. The patterning (local desorption) of SAMs from alkane thiols on gold was performed by scanning electrochemical microscopy (SECM), followed by the assembly of an amino-deriva-tized disulfide and coupling of glucose oxidase to form a catalytically active pattern of the enzyme. The enzymatic activity could be monitored/imaged by SECM. 

Scheme 4 Schematic of scanning electrochemical microscopy-double potential step chromoamperometry (SECM-DPSC) measurements, (a) In the forward step, Bt2 is produced via the oxidation of Br . (b) At tswitch. the potential is reversed to collect Br2 by reduction to Br. ...

Nanostructured materials have also been formed by scanning tunneling microscopy (STM) [24], scanning electrochemical microscopy (SECM) [25], and atomic force microscopy (AFM) [26], Recent reports on the modification of atomic sites at bare surfaces by STM [27] and the formation of nanometer-scale defects by STM [28] and AFM [29] illustrate the power of these techniques. 

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