Physicochemical study of the 'anatase/electrolyte solution' interface in suspension and closely packed particles of the solid

• Published in: Surface and interface analysis 2011-07, Vol.43 (7), p.1074-1081
• Main Authors: Kamarianakis, George, Tsevis, Athanasios, Spanos, Nikos
• Format: Article
• Language: English
• Subjects: Analytical chemistry; Anatase; Chemistry; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Contact; Electrochemical methods; Electrolytes; Electronic structure and electrical properties of surfaces, interfaces, thin films and low-dimensional structures; Exact sciences and technology; ionic mobility; Physics; Porosity; pzc; Streaming potential; Surface charge; surface conductivity; Surface conductivity and carrier phenomena; Titration; ζ-potential
• ISSN: 0142-2421; 1096-9918; 1096-9918
• DOI: 10.1002/sia.3696

The electric double layer (EDL) developed at the interface of anatase in contact with aqueous electrolyte solutions was investigated at 25 °C. Potentiometric titrations (PT), measurements of the electrophoretic mobility (EM) in suspensions, and streaming potential (SP) measurements were taken. The surface charge over a wide pH range (ca. 3–10) and the point of zero charge (pzc = 6.3 ± 0.1) of anatase was easily determined by means of the suspension titration curve and the blank one, obtained at a single ionic strength value. Streaming potential measurements were conducted in anatase particles appropriately packed to form plugs. Two different plugs were prepared differing in the degree of particles' packing and, consequently, in the respective porosities. It was found that surface conductivity is lower at higher packing (lower porosity), because of the reduction of the total surface area in contact with the electrolyte. Moreover, it was found that the surface conductivity of the anatase samples increased at pH values away from pzc, while the mobility of the counter ions behind the shear plane decreased. This trend was attributed to the increase of the absolute surface charge. This increase caused an increase in the amount of the counter ions and, therefore, in the conductivity due to these ions. On the other hand, stronger electrostatic interactions between the surface of the solid and the counter ions reduced their mobility. The packing density of the anatase particles in the respective plugs, affected the values of ζ‐potential calculated from SP measurements when the effect of surface conductivity was neglected. Copyright © 2010 John Wiley & Sons, Ltd.