Evolution of the electrical double layer with electrolyte concentration probed by second harmonic scattering.

Investigating the electrical double layer (EDL) structure has been a long-standing challenge and has seen the emergence of several sophisticated techniques able to probe selectively the few molecular layers of a solid/water interface. While a qualitative estimation of the thickness of the EDL can be obtained using simple theoretical models, following experimentally its evolution is not straightforward and can be even more complicated in nano- or microscale systems, particularly when changing the ionic concentration by several orders of magnitude. Here, we bring insight into the structure of the EDL of SiO nanoparticle suspensions and its evolution with increasing ionic concentration using angle-resolved second harmonic scattering (AR-SHS).

Water Orientation at the Anatase TiO Nanoparticle Interface: A Probe of Surface p Values.

The acid-base properties of surfaces significantly influence catalytic and (photo)electrochemical processes. Estimation of acid dissociation constants (p values) for colloids is commonly performed through electroanalytical techniques or spectroscopic methods employing label molecules. Here, we show that polarimetric angle-resolved second harmonic scattering (AR-SHS) can be used as an all-optical, label-free probe of colloid surface p values.

Second Harmonic Scattering Reveals Ion-Specific Effects at the SiO and TiO Nanoparticle/Aqueous Interface.

Ion-specific effects play a crucial role in controlling the stability of colloidal systems and regulating interfacial processes. Although mechanistic pictures have been developed to explain the electrostatic structure of solid/water colloidal interfaces, ion-specific effects remain poorly understood. Here we quantify the average interfacial water orientation and the electrostatic surface potential around 100 nm SiO and TiO colloidal particles in the presence of NaCl, RbCl, and CaCl using polarimetric angle-resolved second harmonic scattering.

Surface Potential and Interfacial Water Order at the Amorphous TiO Nanoparticle/Aqueous Interface.

Colloidal nanoparticles exhibit unique size-dependent properties differing from their bulk counterpart, which can be particularly relevant for catalytic applications. To optimize surface-mediated chemical reactions, the understanding of the microscopic structure of the nanoparticle-liquid interface is of paramount importance. Here we use polarimetric angle-resolved second harmonic scattering (AR-SHS) to determine surface potential values as well as interfacial water orientation of ∼100 nm diameter amorphous TiO nanoparticles dispersed in aqueous solutions, without any initial assumption on the distribution of interfacial charges.

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 SiO colloidal suspensions to experimentally determine both surface potential and interfacial water orientation as a function of pH and NaCl concentration.