Monte Carlo modeling of ion adsorption at the energetically heterogeneous metal oxide/electrolyte interface: Micro- and macroscopic correlations between adsorption energies

Effective adsorption energy distribution function as a new mean-field characteristic of surface heterogeneity in adsorption systems with lateral interactions

“…According to Piasecki [25], the electrostatic interactions can mimic the surface heterogeneity. A similar conclusion can be drown from the recent grand canonical Monte Carlo simulations of proton uptake/release [10] as well as the electrolyte ion adsorption on heterogeneous metal oxide surfaces [9]. The simulation of different topologies/topographies has shown that the lateral repulsive interactions mask effectively almost all surface properties (occurring inside the screening range).…”

“…However, the long-range interactions of a range comparable to or higher than the patch size made the isotherms smooth [10]. A similar shielding effect of electrostatic interactions is observed if micro/macroscopic correlations between adsorption energies are considered [9]. Moreover, the adsorption isotherm for a highly heterogeneous system neglecting electrostatics and the isotherm for a homogeneous system including lateral repulsive interactions could be indistinguishable (for certain values of interaction/heterogeneity parameters) [26].…”

“…In many actual cases, the quasi-Gaussian function is considered as the best approximation [3,6]. In the case discussed here, the quasiGaussian distribution function (for the considered interface denoted by Γ ) can be written in the form [9,26] (pK = − log(K) and pK ∼ ε):…”

“…The most important is that the IAI solution is a mean-field type, so the local correlations cannot be considered [8,9]. In other words, AEDF does not describe the surface topography and topology, so the real nature of the surface heterogeneity (surface position dependence of adsorption energy) is treated in the average (meanfield) way [7][8][9][10].…”

“…The most important is that the IAI solution is a mean-field type, so the local correlations cannot be considered [8,9]. In other words, AEDF does not describe the surface topography and topology, so the real nature of the surface heterogeneity (surface position dependence of adsorption energy) is treated in the average (meanfield) way [7][8][9][10]. Nevertheless, IAI is still one of the most popular methodologies for describing adsorption on heterogeneous surfaces, especially if the simple analytical model for fitting experimental data is required [3,6,11].…”