Separating Hofmeister Trends in Stern and Diffuse Layers at a Charged Interface

Understanding the role of pH and ions on the electrical double layer (EDL) at charged mineral oxide/aqueous interfaces remains crucial in modeling environmental and industrial processes. Yet the simultaneous contribution of pH and specific ion effects (SIEs) on the different layers of the EDL remains unknown. Here, we utilize zeta potential measurements, vibrational sum frequency generation, and the maximum entropy method to ascertain the detailed structure of the Stern and diffuse regions of the EDL at the silica/water interface with varying pH values for different alkali chlorides. Both at pH 2, when the surface is nearly neutral, and at pH 12, when the surface is highly charged, we observe that Li⁺ and Na⁺ disrupt while Cs⁺ enhances existing water structures within the Stern layer. Moreover, the SIE trends for the diffuse and Stern layers are opposite to one another at pH 2 (in the amount of ordered water) and at pH 12 (in the amount of net oriented water). Finally, we observe an inversion in Hofmeister (SIE) trends at low and high pH in the zeta that impacts the diffuse layer structure. These results indicate that SIEs play critical yet separable roles in governing both the electrostatic and water-structuring capabilities of the EDL.