Water at charged interfaces

Abstract

The ubiquity of aqueous solutions in contact with charged surfaces and the realization that the molecular-level details of water-surface interactions often determine interfacial functions and properties relevant in many natural processes have led to intensive research. Even so, many open questions remain regarding the molecular picture of the interfacial organization and preferential alignment of water molecules, as well as the structure of water molecules and ion distributions at different charged interfaces. While water, solutes and charge are present in each of these systems, the substrate can range from living tissues to metals. This diversity in substrates has led to different communities considering each of these types of aqueous interface. In this Review, by considering water in contact with metals, oxides and biomembranes, we show the essential similarity of these disparate systems. While in each case the classical mean-field theories can explain many macroscopic and mesoscopic observations, it soon becomes apparent that such theories fail to explain phenomena for which molecular properties are relevant, such as interfacial chemical conversion. We highlight the current knowledge and limitations in our understanding and end with a view towards future opportunities in the field.

Influence of an electrified interface on the entropy and energy of solvation of methanol oxidation intermediates on platinum(111) under explicit solvation

“…The higher mobilities of the H 2 O molecules under thermal-catalytic conditions is because the field influences the H 2 O structure (see ref. 41 and 91–93 and Fig. 6).…”

Effects of stearyl alcohol monolayer on the structure, dynamics and vibrational sum frequency generation spectroscopy of interfacial water

“…Vibrational sum frequency generation (VSFG) spectroscopy provides an efficient tool to probe interfacial regions at the molecular level even for buried interfaces that are accessible by light. [16][17][18][19][20][21][22][23][24][25][26][27][28] The VSFG response comes from the monolayer or submonolayer interfacial regions and it normally does not pick up contributions from the bulk phase due to its centrosymmetric nature. For the air-water interface, the response becomes complicated due to intra-and intermolecular coupling between O-H oscillators.…”

“…In addition to pure water-air interfaces, the VSFG spectroscopy of the OH stretch modes of water has also been used for studies of aqueous interfaces with a variety of complex solutes. [17][18][19][20][34][35][36][37][38][39][40] Apart from the OH stretch modes of water, there have also been studies where the VSFG spectrum in the C-H stretching region has also been connected to the order/disordered monolayer and orientation of alkyl groups of alcohols, lipids and other organic substances at aqueous surfaces. [40][41][42][43] In a recent work, 44 we investigated the interfacial behavior of water covered by a layer of tertiary butyl alcohol (TBA) which carries a fully branched hydrophobic part.…”

In Situ Investigation on Life‐Time Dynamic Structure–Performance Correlation Toward Electrocatalyst Service Behavior in Water Splitting

“…The water molecular behavior at the interface is much different from that in the liquid phase, which has led to a lot of study about interfacial water science. [54][55][56] In water electrocatalysis, the specific water structure at charged electrode interface, such as its orientation and hydrogen-bonding network, will significantly affect the reaction mechanism and activity. [57] Therefore, the detailed characterization of interfacial water structures is key to revealing configuration-related activity.…”