Evolution of Interfacial Hydration Structure Induced by Ion Condensation and Correlation Effects

TL;DR

This study uses advanced microscopy and simulations to reveal how multivalent ions induce concentration-dependent changes in interfacial hydration structures, impacting various applications like batteries and colloids.

Contribution

First experimental observation of interfacial hydration structures at molecular resolution for multivalent ions, revealing their evolution with concentration and correlation effects.

Findings

Layer number varies from 2 to 1 and back to 2 with concentration.

Interlayer thickness increases from 0.25 to 0.34 nm.

Hydration force increases significantly with concentration.

Abstract

Interfacial hydration structures are crucial in wide-ranging applications, including battery, colloid, lubrication etc. Multivalent ions like Mg2+ and La3+ show irreplaceable roles in these applications, which are hypothesized due to their unique interfacial hydration structures. However, this hypothesis lacks experimental supports. Here, using three-dimensional atomic force microscopy (3D-AFM), we provide the first observation for their interfacial hydration structures with molecular resolution. We observed the evolution of layered hydration structures at La(NO3)3 solution-mica interfaces with concentration. As concentration increases from 25 mM to 2 M, the layer number varies from 2 to 1 and back to 2, and the interlayer thickness rises from 0.25 to 0.34 nm, with hydration force increasing from 0.27+-0.07 to 1.04+-0.24 nN. Theory and molecular simulation reveal that multivalence induces concentration-dependent ion condensation and correlation effects, resulting in compositional and structural evolution within interfacial hydration structures. Additional experiments with MgCl2-mica, La(NO3)3-graphite and Al(NO3)3-mica interfaces together with literature comparison confirm the universality of this mechanism for both multivalent and monovalent ions. New factors affecting interfacial hydration structures are revealed, including concentration and solvent dielectric constant. This insight provides guidance for designing interfacial hydration structures to optimize solid-liquid-interphase for battery life extension, modulate colloid stability and develop efficient lubricants.