Probing consequences of anion-dictated electrochemistry on the electrode/monolayer/electrolyte interfacial properties

Altering electrochemical interfaces by using electrolyte effects or so-called “electrolyte engineering” provides a versatile means to modulate the electrochemical response. However, the long-standing challenge is going “beyond cyclic voltammetry” where electrolyte effects are interrogated from the standpoint of the interfacial properties of the electrode/electrolyte interface. Here, we employ ferrocene-terminated self-assembled monolayers as a molecular probe and investigate how the anion-dictated electrochemical responses are translated in terms of the electronic and structural properties of the electrode/monolayer/electrolyte interface. We utilise a photoelectron-based spectroelectrochemical approach that is capable of capturing “snapshots” into (1) anion dependencies of the ferrocene/ferrocenium (Fc/Fc + ) redox process including ion-pairing with counter anions (Fc + –anion) caused by differences in Fc + –anion interactions and steric constraints, and (2) interfacial energetics concerning the electrostatic potential across the electrode/monolayer/electrolyte interface. Our work can be extended to provide electrolyte-related structure-property relationships in redox-active polymers and functionalised electrodes for pseudocapacitive energy storage. Conveying electrochemistry in terms of the electrode/electrolyte interfacial properties remains challenging. Here, the authors employ a surface-bound molecular probe and photoelectron spectroscopy to peer into the anion-dictated and potential-induced interfacial electronic and structural properties.