In Section 3.2, the implications of solvation of the immobilized moiety in an electrochemical redox reaction were discussed. The preference for solvation of the surface-attached cobalt complex in acetonitrile caused it to stay outside the electron double layer, where an outer-sphere, redox-mediated, stepwise mechanism for hydrogen evolution reaction occurs. On the contrary, poor solvation of the same immobilized catalyst in an aqueous electrolyte forced it to stay within the double layer and be stabilized by additional interactions with the surface (axial coordination and π-π stacking). As a result, a disparate reaction mechanism bypassing redox-mediation was observed (Figure ). In the previous section, we discussed the investigation of electric field-induced electrostatic interaction in an insulated cell for non-redox reactions and emphasized the uniqueness and advantages of the parallel plate cell design. However, it is also imperative to understand the impact of local electric fields in an electric cell where a continuous current is supplied to catalyze electrochemical transformations. For instance, alkali metals can increase the accumulation of CO2 at the electrode, therefore, facilitate the reduction rate by increasing the local concentration of CO2. The electric field generated by ions/charges is proven to stabilize key intermediates in the transformation as well. Those findings suggest a different angle of viewing the implication of the molecular structure (ligand + substituents) when designing a chemically modified electrode for electrochemical reactions: instead of focusing on the change of the redox potential of the catalyst, modifying the molecular structure in combination with the metal identity and local environment (electrolyte composition, solvent, etc.) may afford a potent catalyst by modulating the binding of key intermediates. Examples supporting this proposed idea will be presented in the next section. However, before utilizing the electric field and introducing electrostatic interactions between the electrode and the attached molecule under current, it is vital to understand and possibly calculate the influence of the interfacial electric field around a molecularly modified electrode under similar circumstances.