The relationship between inner surface potential and electrokinetic potential from an experimental and theoretical point of view*
Tajana Preočanin A D , Danijel Namjesnik A , Matthew A. Brown B and Johannes Lützenkirchen C
+ Author Affiliations
- Author Affiliations
A Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia.
B Laboratory for Surface Science and Technology, Department of Materials, Swiss Federal Institute of Technology (Eidgenössische Technische Hochschule) Zürich, CH-8093 Zurich, Switzerland.
C Institut für Nukleare Entsorgung (INE), Karlsruher Institut für Technologie (KIT), Postfach 3640, 76021 Karlsruhe, Germany.
D Corresponding author. Email: tajana@chem.pmf.hr
Environmental Chemistry 14(5) 295-309 https://doi.org/10.1071/EN16216
Submitted: 28 December 2016 Accepted: 5 April 2017 Published: 3 May 2017
Environmental context. Interfacial properties of colloid and nanoparticles are directly related to the reactivity and surface densities of existing surface sites. Surface characterisation of particles provides only some kind of average surface properties. Analysis of well-defined monocrystal surfaces, which form the surface of the single particle, leads to a better understanding of surface reactions and mutual interactions of adjacent crystal planes on average surface properties.
Abstract. The contact of small solid particles and macroscopic flat planes with aqueous electrolyte solutions results in the accumulation of ions at the interface and the formation of the electrical interfacial layer. Analysis of well-defined monocrystal surfaces, which are the building blocks of a single particle, leads to a better understanding of surface reactions and mutual interactions of adjacent crystal planes on average surface properties of particles. We analyse inner surface potential (obtained by single-crystal electrode) and zeta-potential data (obtained by streaming potential measurements) that were obtained on identical samples. Among the systems for which comparable surface and zetapotentials are available, measured inner surface potential data for sapphire (0001), haematite (0001) and rutile (110) show the expected behaviour based on the face-specific surface chemistry model, whereas the slopes for rutile (110) and quartz (0001) do not. Isoelectric points for sapphire (0001), haematite (0001) and rutile (100) are in conflict with the standard model that implies consistent behaviour of surface potential and diffuse layer potential. For the two former systems, previous results from the literature suggest that the charge of interfacial water can explain the discrepancy. The water layer could also play a role for quartz (0001), but in this case, the discrepancy would simply not be noticed, because both point of zero potential and isoelectric point are low. Along with data on silver halides, it can be concluded that six-ring water structures on solids may generate the electrokinetic behaviour that is typical of inert surfaces like Teflon.
Additional keywords: electrical interfacial layer, haematite, interfacial water, quartz, rutile, sapphire, silica, single-crystal electrodes, streaming potential.
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