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.
Keywords: electric field-assisted catalysis; electrocatalysis; electrode surface; functionalized electrode; integrated catalysis; organometallic complex; surface functionalization; switchable catalysis.