Molecular Nature of Structured Water in the Light-Induced Interfacial Capacitance Changes at the Bioelectric Interface

Uncovering the function of structured water in the interfacial capacitance at the molecular level is the basis for the development of the concept and model of the electric double layer; however, the limitation of the available technology makes this task difficult. Herein, using surface-enhanced infrared absorption spectroscopy combined with electrochemistry, we revealed the contribution of the cleavage of loosely bonded tetrahedral water to the enhancement of model membrane capacitance. Upon further combination with ionic perturbation, we found that the interface hydrogen bonding environment in the stern layer was greatly significant for the light-induced cleavage of tetrahedral water and thus the conversion of optical signals into electrical signals. Our work has taken an important step toward gaining experimental insight into the relationship between water structure and capacitance at the bioelectric interface

Uncovering the Dominant Role of an Extended Asymmetric Four-Coordinated Water Network in the Hydrogen Evolution Reaction

In situ and accurate measurement of the structure and dynamics of interfacial water in the hydrogen evolution reaction (HER) is a well-known challenge because of the coupling of water among varied structures and its dual role as reactants and solvents. Further, the interference of bulk water and intricate interfacial interactions always hinders the probing of interfacial water. Surface-enhanced infrared absorption spectroscopy is extremely sensitive for the measurement of interfacial water; herein, we develop a nanoconfinement strategy by introducing nonaqueous ionic liquids to decouple and tailor the water structure in the electric double layer and further combined with molecular dynamics simulations, successfully gaining the correlation between isolated water, water clusters, and the water network with HER activity. Our results clearly disclosed that the potential-dependent asymmetric four-coordinated water network, whose connectivity could be regulated by hydrophilic and hydrophobic cations, was positively correlated with HER activity, which provided a pioneering guidance framework for revealing the function of water in catalysis, energy, and surface science