Scanning electrochemical potential microscopy

Hurth, C. Li, C. Bard, A. J. Direct probing of electrical double layers by scanning electrochemical potential microscopy. J Phys Chem C 2007, 111, 4620-4627. 

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. 

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. ...

As described in the introduction, submicrometer disk electrodes are extremely useful to probe local chemical events at the surface of a variety of substrates. However, when an electrode is placed close to a surface, the diffusion layer may extend from the microelectrode to the surface. Under these conditions, the equations developed for semi-infinite linear diffusion are no longer appropriate because the boundary conditions are no longer correct [97]. If the substrate is an insulator, the measured current will be lower than under conditions of semi-infinite linear diffusion, because the microelectrode and substrate both block free diffusion to the electrode. This phenomena is referred to as shielding. On the other hand, if the substrate is a conductor, the current will be enhanced if the couple examined is chemically stable. For example, a species that is reduced at the microelectrode can be oxidized at the conductor and then return to the microelectrode, a process referred to as feedback. This will occur even if the conductor is not electrically connected to a potentiostat, because the potential of the conductor will be the same as that of the solution. Both shielding and feedback are sensitive to the diameter of the insulating material surrounding the microelectrode surface, because this will affect the size and shape of the diffusion layer. When these concepts are taken into account, the use of scanning electrochemical microscopy can provide quantitative results. For example, with the use of a 30-nm conical electrode, diffusion coefficients have been measured inside a polymer film that is itself only 200 nm thick [98]. 

Since micro-gravimetry with the EQCM lacks specificity only the difference of cation and anion fluxes can be obtained by microgravimetry and therefore an independent measurement of specific ions is needed. Scanning electrochemical microscopy (SECM) coupled with a quartz crystal microbalance with independent potential control of the tip and substrate has been recently done by Cliffel and Bard [28]. In this experiment generation at the substrate (EQCM crystaj) working electrode and collection at the tip of an ultramicroelectrode (UNE) that was approached perpendicular to the EQCM crystal was employed with measurement of A/. Hillier and Ward [8] had previously used a scanning microelectrode to map the mass sensitivity across the surface of the QCM crystal. Reflection of longitudinal waves at the UME tip limits these experiments due to oscillations. 

Formation or consumption of reacting species at the electrode surface causes concentration distribution of electroactive species in the solution phase during electrolysis. Equi-concentration contours stand for a concentration profile. A concentration profile can be measured by detecting current or potential by use of a small probe electrode at various locations near a target large electrode. A typical method is scanning electrochemical microscopy. See also diffusion layer, - scanning electrochemical microscope. 

The time range of the electrochemical measurements has been decreased considerably by using more powerful -> potentiostats, circuitry, -> microelectrodes, etc. by pulse techniques, fast -> cyclic voltammetry, -> scanning electrochemical microscopy the 10-6-10-1° s range has become available [iv,v]. The electrochemical techniques have been combined with spectroscopic ones (see -> spectroelectrochemistry) which have successfully been applied for relaxation studies [vi]. For the study of the rate of heterogeneous -> electron transfer processes the ILIT (Indirect Laser Induced Temperature) method has been developed [vi]. It applies a small temperature perturbation, e.g., of 5 K, and the change of the open-circuit potential is followed during the relaxation period. By this method a response function of the order of 1-10 ns has been achieved. 

A recent introduction of scanning electrochemical microscopy (SECM) to this field [16-23] has revitalized the study of ET at the OAV interface. In contrast to the conventional, four-electrode cyclic voltammetry at externally polarized OAV interfaces, the SECM measurements not necessarily require supporting electrolytes, and thus can be carried out over a wide range of driving forces without the limitation of the potential window. This advantage of SECM allowed for an experimental verification of the Marcus theory in the driving-force dependence of the ET rate constant [18,21]. 

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...

Scanning tunnelling microscopy, scanning electrochemical microscopy, and AFM-surface potential measurements have also been used to investigate Nafion films. Scanning electrochemical microscopy reveals a domain-like structure containing circular features ca. 1-2 nm in diameter made up of a conductive center (presumed to be ion-rich regions) surrounded by a much less conductive zone. " Atomic force microscopy surface potential measurements detect features that were interpreted as ion channels in Nafion membranes. The size of the claimed ion channels was... 

A few years ago Bard and his group developed the technique called scanning electrochemical microscopy (SECM) which makes possible a spatial analysi,s of charge transfer processes [9]. In this method an additional tip electrode of a diameter of about 2 pm is used as well as the three other electrodes (semiconductor, counter and reference electrode). Assuming that a redox system is reduced at the semiconductor, then the reduced species can be re-oxidized at the tip electrode, the latter being polarized positively with respect to the redox potential. The corresponding tip current / [ is proportional to the local concentration of the product formed at the semiconductor surface and therefore also to the corresponding local semiconductor current, provided... 

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