Anomalous interfacial dynamics of single proton charges in binary aqueous solutions

Understanding the dynamics of charge exchange between a solid surface and a liquid is fundamental to various situations, ranging from nanofiltration to catalysis and electrochemistry. Charge transfer is ultimately determined by physicochemical processes (surface group dissociation, ion adsorption, etc...) occurring in the few layers of molecules at the interface between the solid and the liquid. Unfortunately, these processes remain largely uncharted due to the experimental challenges in probing interfacial charge dynamics with sufficiently high spatial and temporal resolution. Here, we resolve at the single-charge scale, the dynamics of proton charges at the interface between an hBN crystal and binary mixtures of water and organic amphiphilic solvents (e.g. alcohol), evidencing a dramatic influence of solvation on interfacial dynamics. Our observations rely on the application of spectral Single Molecule Localization Microscopy (sSMLM) to two types of optically active defects at the hBN surface, which act as intrinsic optical markers for both surface protonation and interaction with apolar alkyl groups of the organic solvent. We use sSMLM to reveal interfacial proton charge transport as a succession of jumps between the titratable surface defects, mediated by the transport of the solvated proton charge along the solid/liquid interface. By changing the relative concentration of water in binary mixtures, we evidence a non-trivial effect on interfacial proton charge dynamics, leading at intermediate water concentration to an increased affinity of the proton charge to the solid surface, accompanied by an increased surface diffusivity. These measurements confirm the strong role of solvation on interfacial proton charge transport and establish the potential of single-molecule localization techniques to probe a wide range of dynamic processes at solid/liquid interfaces.