Summary. The importance of the electrode surface structure in electrochemistry is briefly described. Examples are given in which the structural information provided by scanning tunneling microscopy (STM) is of assistance in clarifying the electrochemical behavior. The importance of surface structure in the photoelectrochemical response of metals is illustrated by an STM application. Finally, the potentialities of new scanning microprobe techniques suitable for mapping local photoelectrochemical properties of metal surfaces are briefly discussed.
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