Nonlinear response of the surface electrostatic potential formed at metal oxide/electrolyte interfaces. A Monte Carlo simulation study
An analysis of surface potential nonlinearity at metal oxide/electrolyte interfaces is presented. By using Grand Canonical Monte Carlo simulations of a simple lattice model of an interface, we show a correlation exists between ionic strength as well as surface site densities and the non-Nernstian response of a metal oxide electrode. We propose two approaches to deal with the 0-nonlinearity: one based on perturbative expansion of the Gibbs free energy and another based on assumption of the pH-dependence of surface potential slope. The theoretical anal ysis based on our new potential form gives excellent performance at extreme pH regions, where classical formulae based on the Poisson-Boltzmann equation fail. The new formula is general and independent of any underlying assumptions. For this reason, it can be directly applied to experimental surface potential measurements, including those for individual surfaces of single crystals, as we present for data reported by Kallay and Preocanin [Kallay, Preocanin J. Colloid and Interface20 Sci. 318 (2008) 290].
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 973703
- Report Number(s):
- PNNL-SA-66514; JCISA5; KC0303020; TRN: US201006%%946
- Journal Information:
- Journal of Colloid and Interface Science, 341(1):143-152, Vol. 341, Issue 1; ISSN 0021-9797
- Country of Publication:
- United States
- Language:
- English
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