Probing the Interface of Microscopic Clay Particles in Aqueous Solution by Second Harmonic Generation

Second harmonic generation (SHG) is applied for the first time to study the surfaces of clay particles. An SHG signal was detected from an aqueous suspension of disk-shaped montmorillonite clay particles of 0.5 μm diameter and 0.01 μm thickness. The origin of the SHG signal is the polarization of water molecules by surface charges located in the edge region of the clay particles. On addition of the organic molecule 4-(2-pyridylazo)resorcinol (PR) to the clay aqueous suspension, a strong SHG signal originating from the PR molecules adsorbed onto the edge surfaces of the clay particles was obtained. The PR adsorbed on the basal planes do not contribute to the SHG signal because of cancellation effects. These experimental results demonstrate the applicability of the SHG method for studying molecular adsorption and the electrostatic properties of clay particles.