LAUSR

The detailed structure of the water layer in the inner Helmholtz plane of a solid/aqueous solution interface is closely related to the electrochemical and catalytic performances of electrode materials. While the applied potential can have a great impact, specifically adsorbed species can also influence the interfacial water structure. With the specific adsorption of p-nitrobenzoic acid on the Au(111) surface, a protruding band above 3600 cm−1 appears in the electrochemical infrared spectra, indicating a distinct interfacial water structure as compared to that on bare metal surfaces, which displays a potential-dependent broad band in the range of 3400–3500 cm−1. Although three possible structures have been guessed for this protruding infrared band, the band assignment and interfacial water structure remain ambiguous in the past two decades. Herein, by combining surface-enhanced infrared absorption spectroscopy and our newly developed quantitative computational method for electrochemical infrared spectra, the protruding infrared band is clearly assigned to the surface-enhanced stretching mode of water molecules hydrogen-bonded to the adsorbed p-nitrobenzoate ions. Water molecules, meanwhile, are hydrogen-bonded with themselves to form chains of five-membered rings. Based on the reaction free energy diagram, we further demonstrate that both hydrogen-bonding interactions and coverages of specifically adsorbed p-nitrobenzoate play an important role in determining the structure of the water layer in the Au(111)/p-nitrobenzoic acid solution interface. Our work sheds light on structural studies of the inner Helmholtz plane under specific adsorptions, which advances the understanding of structure–property relationships in electrochemical and heterogeneous catalytic systems.