Mapping dynamic concentration profiles with micrometric resolution near anactive microscopic surface by confocal resonance Raman microscopy. Application to diffusion near ultramicroelectrodes: first direct evidence for a conproportionation reaction

Confocal Raman microspectroscopy is a very efficient means for probing the molecular composition of micrometric-sized samples. Its coupling with Raman resonance spectroscopy allows the specific tracking of very dilute species by considerably enhancing its Raman bands. Thus, spatially resolved inform ation on the chemical composition of diffusion layers, which build up spont aneously near an active surface placed in a solution, can be obtained with a micrometric resolution. In this work, the applicability of the method for imaging diffusional transport towards ultramicroelectrodes with a micromet ric resolution is examined. The efficiency and versatility of confocal reso nance Raman microspectroscopy have been tested by probing the composition o f the two different diffusion layers which build up in the vicinity of an u ltramicroelectrode during the reduction of tetracyanoquinodimethane (TCNQ) on its first or second electrochemical wave. Besides the establishment of t he method, this work affords the first direct experimental evidence of the existence and role of conproportionation reactions, which take place on the second reduction wave of EE electrochemical systems. In both cases, the co ncentration profiles of the radical anion TCNQ(.-) agree extremely well wit h the theoretical predictions. (C) 2000 Elsevier Science S.A. All rights re served.