Probing using scanning electrochemical

Bolt, F. M., Bakes, N., Borgwarth, K., Heinze, J. Investigation of carboxylic-functionalized and -aUcanethiol self-assembled monolayers on gold and their application as pH-sensitive probes using scanning electrochemical microscopy. Surf. Sci. 2005, 597, 51-64. 

The first micro-ITIES were introduced in 1986, using a glass micropipette which was pulled down to a fine tip of around 25 pm to support the interface [66-71]. The smaller size of micropipettes or microcapillaries is advantageous for sensor applications, providing the possibility of studying microenvironments as living cells, and it can also be used as a probe in scanning electrochemical microscopy (SECM) [72]. 

B. Lin, R. Hu, C. Ye, Y. Li, C. Lin, A study on the initiation of pitting corrosion in carbon steel in chloride-containing media using scanning electrochemical probes, Electrochim. Acta 55 (2010)... 

An attempt was made to model the interfacial chemistry in microemulsions by using the interface between two immiscible electrolyte solutions [95]. The reaction between the electrochemically generated Co(I) form of vitamin B12 in the aqueous phase and /-DBCH in benzonitrile was probed directly at the interface by using scanning electrochemical microscopy. The kinetics of /-DBCH reduction by vitamin B12 was observed to be more complex at the liquid/liquid interface than in a homogeneous solution [95]. 

Ishimatsu R, Kim J, ling P, Striemer CC, Fang DZ, Fauchet PM et al (2010) Ion-selective permeability of an ultrathin nanoporous silicon membrane as probed by scanning electrochemical microscopy using micropipet-supported ITIES tips. Anal Chem 82(17) 7127-7134. doi 10.1021/acl005052... 

Ishimatsu, R., J. Kim, P. ling, C. C. Striemer, D. Z. Fang, P. M. Fauchet, J. L. McGrath, and S. Amemiya, Ion-selective permeability of a ultrathm nanopore silicon membrane as probed by scanning electrochemical microscopy using micropipet-supported fTIES tips. Anal. Chem., Vol. 82, 2010 pp. 7127-7134. 

Scanning electrochemical microscopy can also be applied to study localized biological activity, as desired, for example, for in-situ characterization of biosensors (59,60). In this mode, the tip is used to probe the biological generation or consumption of electroactive species, for example, the product of an enzymatic surface reaction. The utility of potentiometric (pH-selective) tips has also been... 

A variety of other techniques have been used to investigate ion transport in conducting polymers. The concentrations of ions in the polymer or the solution phase have been monitored by a variety of in situ and ex situ techniques,8 such as radiotracer studies,188 X-ray photoelectron spectroscopy (XPS),189 potentiometry,154 and Rutherford backscatter-ing.190 The probe-beam deflection method, in which changes in the density of the solution close to the polymer surface are monitored, provides valuable data on transient ion transport.191 Rotating-disk voltammetry, using an electroactive probe ion, provides very direct and reliable data, but its utility is very limited.156,19 193 Scanning electrochemical microscopy has also been used.194... 

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. 

The kinetics of AgGl dissolution in aqueous solutions without supporting electrolyte have been studied utilizing well-defined and high mass transport properties of the scanning electrochemical microscope [376]. An ultramicroelectrode probe positioned close to the AgGl surface was used to induce and monitor dissolution of the salt via reduction of Ag+ from the initially saturated solution. 

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]. 

Scanning electrochemical microscopy (SECM the same abbreviation is also used for the device, i.e., the microscope) is often compared (and sometimes confused) with scanning tunneling microscopy (STM), which was pioneered by Binning and Rohrer in the early 1980s [1]. While both techniques make use of a mobile conductive microprobe, their principles and capabilities are totally different. The most widely used SECM probes are micrometer-sized ampero-metric ultramicroelectrodes (UMEs), which were introduced by Wightman and co-workers 1980 [2]. They are suitable for quantitative electrochemical experiments, and the well-developed theory is available for data analysis. Several groups employed small and mobile electrochemical probes to make measurements within the diffusion layer [3], to examine and modify electrode surfaces [4, 5], However, the SECM technique, as we know it, only became possible after the introduction of the feedback concept [6, 7],... 

The SECM can be used in the feedback mode to probe lateral mass-charge transfer [79-83]. The theory of SECM feedback surveyed in Section IV.A.2 assumes that the substrate surface is uniformly reactive. When lateral mass and/ or charge transfer occurs on the substrate surface, or within a thin film, the surface reactivity of the substrate becomes non-uniform and the SECM feedback theory must be modified. Unwin and Bard [79] developed the theory for adsorption-desorption of a redox species at the substrate that allowed for surface diffusion of the adsorbate. They introduced a new approach, the scanning electrochemical microscope induced desorption (SECMID), as a way to probe surface diffusion. The set of differential equations for the diffusion problem comprise Eqs. (8a,b), and Eq. (26), which relates the redox concentration at the substrate surface and the surface coverage by adsorbed species... 

Scanning electrochemical microscopy seeks to overcome the lack of sensitivity and selectivity of the probe tip in STM and AFM to the substrate identity and chemical composition. It does this by using both tip and substrate as independent working electrodes in an electrochemical cell, which therefore also includes auxiliary and reference electrodes. The tip is a metal microelectrode with only the tip active (usually a metal wire in a glass sheath). At large distances from the substrate, in an electrolyte solution containing an electroactive species the mass-transport-limited current is therefore... 

For the investigation of electrode reaction parameters and chemistry at these dimensions, another approach is necessary, in order to make the system species-selective through monitoring the electrochemistry. This involves making tip and substrate into independent electrodes the tip is thus a microelectrode. The microelectrode tip is scanned over the surface this is known as scanning electrochemical microscopy (SECM) [43] and due to its local probe nature can be used to probe microvolumes. 

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. 

Scanning electrochemical microscopy (SECM) [196] is a member of the growing family of scanning probe techniques. In SECM the tip serves as an ultramicroelectrode at which, for instance, a radical ion may be generated at very short distances from the counterelectrode under steady-state conditions. The use of SECM for the study of the kinetics of chemical reactions following the electron transfer at an electrode [196] involves the SECM in the so-... 

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