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Title: Nonlinear response of the surface electrostatic potential formed at metal oxide/electrolyte interfaces. A Monte Carlo simulation study

Abstract

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].

Authors:
;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
973703
Report Number(s):
PNNL-SA-66514
Journal ID: ISSN 0021-9797; JCISA5; KC0303020; TRN: US201006%%946
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Colloid and Interface Science, 341(1):143-152; Journal Volume: 341; Journal Issue: 1
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ELECTROSTATICS; FREE ENTHALPY; ELECTROLYTES; OXIDES; INTERFACES; PERFORMANCE; SURFACE POTENTIAL; NONLINEAR PROBLEMS; MONTE CARLO METHOD

Citation Formats

Zarzycki, Piotr P., and Rosso, Kevin M.. Nonlinear response of the surface electrostatic potential formed at metal oxide/electrolyte interfaces. A Monte Carlo simulation study. United States: N. p., 2010. Web. doi:10.1016/j.jcis.2009.09.002.
Zarzycki, Piotr P., & Rosso, Kevin M.. Nonlinear response of the surface electrostatic potential formed at metal oxide/electrolyte interfaces. A Monte Carlo simulation study. United States. doi:10.1016/j.jcis.2009.09.002.
Zarzycki, Piotr P., and Rosso, Kevin M.. Fri . "Nonlinear response of the surface electrostatic potential formed at metal oxide/electrolyte interfaces. A Monte Carlo simulation study". United States. doi:10.1016/j.jcis.2009.09.002.
@article{osti_973703,
title = {Nonlinear response of the surface electrostatic potential formed at metal oxide/electrolyte interfaces. A Monte Carlo simulation study},
author = {Zarzycki, Piotr P. and Rosso, Kevin M.},
abstractNote = {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].},
doi = {10.1016/j.jcis.2009.09.002},
journal = {Journal of Colloid and Interface Science, 341(1):143-152},
number = 1,
volume = 341,
place = {United States},
year = {Fri Jan 01 00:00:00 EST 2010},
month = {Fri Jan 01 00:00:00 EST 2010}
}