Flow-induced surface charge heterogeneity in electrokinetics due to Stern-layer conductance coupled to reaction kinetics

Abstract

We theoretically study the electrokinetic problem of a pressure-induced liquid flow through a narrow long channel with charged walls, going beyond the classical Helmholtz-Schmolukowski picture by considering the surprisingly strong combined effect of (i) Stern layer conductance and (ii) dynamic charge-regulating rather than fixed surface charges. We find that the water flow induces, apart from the well-known streaming potential, also a strongly heterogeneous surface charge and zeta-potential on chemically homogeneous channel walls. Moreover, we identify a novel steady state with a nontrivial 3D electric flux with 2D surface charges acting as sources and sinks. For a pulsed pressure drop our findings also provide a first-principles explanation for ill-understood experiments on the effect of flow on interfacial chemistry [D. Lis et al., Science 344, 1138 (2014)].