Scanning electrochemical probe microscopy (SEPM) techniques
can
disclose the local electrochemical reactivity of interfaces in single-entity
and sub-entity studies. Operando SEPM measurements consist of using
a SEPM tip to investigate the performance of electrocatalysts, while
the reactivity of the interface is simultaneously modulated. This
powerful combination can correlate electrochemical activity with changes
in surface properties, e.g., topography and structure, as well as
provide insight into reaction mechanisms. The focus of this review
is to reveal the recent progress in local SEPM measurements of the
catalytic activity of a surface toward the reduction and evolution
of O2 and H2 and electrochemical conversion
of CO2. The capabilities of SEPMs are showcased, and the
possibility of coupling other techniques to SEPMs is presented. Emphasis
is given to scanning electrochemical microscopy (SECM), scanning ion
conductance microscopy (SICM), electrochemical scanning tunneling
microscopy (EC-STM), and scanning electrochemical cell microscopy
(SECCM).
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