The use of molecularly
modified electrodes in catalysis heralds
a new paradigm in designing chemical transformations by allowing control
of catalytic activity. Herein, we provide an overview of reported
methods to develop electrodes functionalized with organometallic complexes
and a summary of commonly used techniques for characterizing the electrode
surface after immobilization. In addition, we highlight the implications
of surface functionalization in catalysis to emphasize the key aspects
that should be considered during the development and optimization
of functionalized electrodes. Particularly, surface–molecule
electronic coupling and electrostatic interactions within a hybrid
system are discussed to present effective handles in tuning catalytic
activity. We envision that this emerging type of hybrid catalytic
system has the potential to combine the advantages of homogeneous
catalysis and heterogeneous supports and could be applied to an expanded
range of transformations beyond energy conversion.