Interfacial forces are modified by the growth of surface nanostructures

Nanostructures formed by chemical reaction can modify the interfacial forces present in aqueous solution near a surface. This study uses force-volume microscopy to explore this phenomenon for the growth of manganese oxide nanostructures on rhodochrosite. The interfacial forces above the oxide nanostructures are dominated by electrostatic repulsion for probe-surface separations greater than ca. 2 nm but are overtaken by van der Waals attraction for shorter distances. Across the investigated pH range 5.0-9.7, the maximum repulsive force occurs 2.4 (±1.1) nm above the oxide nanostructures. The magnitude of the repulsive force decreases from pH 5.0 to 6.5, reaches its minimum at 6.5, and then increases steadily up to pH 9.7. Specifically, f _max(pN) = 23(±4)[6.8(±2.1 ) - pH] for pH < 6.5 and f_max(pN) = 19(±2)[pH - 6.1(±1.0)] for pH ≥ 6.5. This dependence indicates that oxide nanostructures have a point of zero charge in the pH range 6-7. In comparison to the nanostructures, the rhodochrosite substrate induces only small interfacial forces in the same pH range, suggesting a neutral orweakly charged surface. The quantitative mapping of interfacial forces, along with the associated influencing factors such as pH or growth of nanostructures, provides a basis for more sophisticated and accurate modeling of processes affecting contaminant immobilization and bacterial attachment on mineral surfaces under natural conditions.