Scanning electrochemical induced desorption

Scanning electrochemical microscopy (SECM) - Direct mode - Feedback mode - Generation/collection mode Scanning reference electrode technique (SRET) Scanning vibrating electrode technique (SVET) Scanning photoelectrochemical microscopy (SPECM) Scanning electrochemical induced desorption (SECMID)... 

For the investigation of adsorption/desorption kinetics and surface diffusion rates, SECM is employed to locally perturb adsorption/desorption equilibria and measure the resulting flux of adsorbate from a surface. In this application, the technique is termed scanning electrochemical induced desorption (SECMID) (1), but historically this represents the first use of SECM in an equilibrium perturbation mode of operation. Later developments of this mode are highlighted towards the end of Sec. II.C. The principles of SECMID are illustrated schematically in Figure 2, with specific reference to proton adsorption/desorption at a metal oxide/aqueous interface, although the technique should be applicable to any solid/liquid interface, provided that the adsorbate of interest can be detected amperometrically. 

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... 

Unwin PR, Bard AJ (1992) Scanning electrochemical microscopy. 14. Scanning electrochemical microscope induced desorption - a new technique for the measurement of adsorption desorption-kinetics and surface-diffusion rates at the solid liquid interface. J Phys Chem 96(12) 5035-5045... 

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