Surface Characterization of Colloidal Silica Nanoparticles by Second Harmonic Scattering: Quantifying the Surface Potential and Interfacial Water Order

The microscopic description of the interface of colloidal particles in solution is essential to understand and predict the stability of these systems, as well as their chemical and electrochemical reactivity. However, this description often relies on the use of simplified electrostatic mean field models for the structure of the interface, which give only theoretical estimates of surface potential values and do not provide properties related to the local microscopic structure, such as the orientation of interfacial water molecules. Here we apply polarimetric angle-resolved second harmonic scattering (AR-SHS) to 300 nm diameter SiO2 colloidal suspensions to experimentally determine both surface potential and interfacial water orientation as a function of pH and NaCl concentration. The surface potential values and interfacial water orientation change significantly over the studied pH and salt concentration range, whereas zeta-potential (ζ) values remain constant. By comparing the surface and ζ-potentials, we find a layer of hydrated condensed ions present in the high pH case, and for NaCl concentrations ≥1 mM. For milder pH ranges (pH < 11), as well as for salt concentrations <1 mM, no charge condensation layer is observed. These findings are used to compute the surface charge densities using the Gouy–Chapman and Gouy–Chapman–Stern models. Furthermore, by using the AR-SHS data, we are able to determine the preferred water orientation in the layer directly in contact with the silica interface. Molecular dynamics simulations confirm the experimental trends and allow deciphering of the contributions of water layers to the total response.


Published in:
The Journal of Physical Chemistry, C123, 33, 20393-20404
Year:
Jul 26 2019
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 Record created 2019-09-19, last modified 2019-09-22


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