Facet-Dependent Surface Charge and Hydration of Semiconducting Nanoparticles at Variable pH

Understanding structure and function of solid-liquid interfaces is essential for the development of nanomaterials for various applications including heterogeneous catalysis in liquid phase processes and water splitting for storage of renewable electricity. The characteristic anisotropy of crystalline nanoparticles is believed to be essential for their performance but remains poorly understood and difficult to characterize. Dual scale atomic force microscopy is used to measure electrostatic and hydration forces of faceted semiconducting SrTiO₃ nanoparticles in aqueous electrolyte at variable pH. The following are demonstrated: the ability to quantify strongly facet-dependent surface charges yielding isoelectric points of the dominant {100} and {110} facets that differ by as much as 2 pH units; facet-dependent accumulation of oppositely charged (SiO₂ ) particles; and that atomic scale defects can be resolved but are in fact rare for the samples investigated. Atomically resolved images and facet-dependent oscillatory hydration forces suggest a microscopic charge generation mechanism that explains colloidal scale electrostatic forces.