Homogeneous catalysis electrochemical methods

From an electrochemical point of view it is easily inferred that the solution in a cell near an electrode is separable into two parts a stagnant layer adjacent to the electrode in which no convective motions occur, and the remainder of the solution, which is homogeneous (bulk solution). Yet this is not a particularity of electrochemical methods since the same phenomena occur at any solid/liquid interface, as when metal particles (reductions by Zn or Na, for example) or any heterogeneous reagent is used in organic homogeneous chemistry, as well as in phase-transfer catalysis or related methods. 

Initially, electrochemical methods were restricted to rather conducting media (solvents with large dielectric constants, large ionic strength), because of problems related to a precise control of an electrode-solution potential difference. Since the rapid development of ultramicroelectrodes in the past decade, this is no more the case, and electrochemistry in solvents of low dielectric constants (arenes, alkanes,efo) or in the absence of deliberately added electrolytes is feasible routinely. Both the theoretical and experimental aspects of such unconventional electrochemistries are now well mastered and the techniques ready for use and application. We have no doubt that the breaking of these historical frontiers of electrochemistry will allow a rich harvest of mechanistic studies performed under conditions that may now approach those used in homogeneous reactions and in catalysis. 

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