Since the electrical double layer (EDL) is where heterogeneous electron transfer occurs, understanding the effects of the electrode-electrolyte interface structure on electrocatalysis is important. The strong electric field in the EDL offers unique environment for electrochemical reactions by altering the solvation structure and mass transport of redox species. Yet, it is challenging to evaluate the physicochemical properties of the matter within EDL, especially for the inner Helmholtz plane (IHP), where most electrochemical reactions occur. This is largely because of the lack of an appropriate model system for experiments. In this talk, the microscopic environment in the IHP of ionic liquids (ILs) is investigated through the reorganization energy reflecting the solvation structure. Exceptionally fast mass transport of Br2 in N-methyl-N-ethyl-pyrrolidinium polybromide allows to obtain bromine reduction voltammograms in which the current plateau is governed by electron-transfer kinetic and to evaluate the reorganization energy based on the Marcus-Hush-Chidsey model. This enables investigation of the microscopic environment in the IHP of the IL affecting electrocatalytic reactions through reorganization energy. As a demonstration, titanium oxide-modified Pt was employed to show pH-dependent reorganization energy, which suggests the switch of major ions at the IHP as a function of surface charges of electrodes. On the other hand, regulating the potential of zero charge (PZC) of electrodes by surface modification and preparation of alloys with various elemental compositions, the surface charge sensitive-ionic structure in ILs is introduced. References Kim, M.; Park, S.; Chung, T. D., Heterogeneous electron transfer reorganization energy at the inner Helmholtz plane in a polybromide redox-active ionic liquid. Chem. Sci. 2022, 13(30), 8821-8828. Kim, M.; Tetteh, E. B.; Savan, A.; Xiao, B.; Ludwig, A.; Schuhmann, W.; Chung, T. D., Reorganization energy in a polybromide ionic liquid measured by scanning electrochemical cell microscopy. J. Chem. Phys. 2023, 158(13), 134707. Kim, M.; Tetteh, E. B.; Krysiak, O. A.; Savan, A.; Xiao, B.; Piotrowiak, T. H.; Andronescu, C.; Ludwig, A.; Chung, T. D.; Schuhmann, W., Acidic Hydrogen Evolution Electrocatalysis at High-Entropy Alloys Correlates with its Composition-Dependent Potential of Zero Charge. Angew. Chem. Int. Ed. 2023, 62(39), e2023100.
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