Structure of the Silica/Divalent Electrolyte Interface: Molecular Insight into Charge Inversion with Increasing pH

The molecular origin of overcharging at mineral oxide surfaces remains a cause of contention within the geochemistry, physics, and colloidal chemistry communities owing to competing chemical versus physical interpretations. Here, we combine vibrational sum frequency spectroscopy and streaming current measurements to obtain molecular and macroscopic insights into the pH-dependent interactions of calcium ions with a fused silica surface. In a 100 mM CaCl2 electrolyte, we observe evidence of charge neutralization at pH similar to 10.5, as deducted from a minimum in the interfacial water signal. Concurrently, adsorption of calcium hydroxide cations is inferred from the appearance of a spectral feature at similar to 3610 cm(-1). However, the interfacial water signal increases at higher pH, while adsorbed calcium hydroxide appears to remain constant, indicating that overcharging results from hydrated Ca2+ ions present within the Stern layer. These findings suggest that both specific adsorption of hydrolyzed ions and ion-ion correlations of hydrated ions govern silica overcharging with increasing pH.