Lateral interactions and enhanced adsorption

Abstract

We extend earlier work on the effects of lateral adsorbate-adsorbate interactions in systems with two different adsorbate species to consider in detail enhanced adsorption phenomena. We give a detailed explanation of the enhancement mechanism for a lattice-gas model in thermodynamic equilibrium, and provide explicit quantitative criteria which must be satisfied by the effective lateral interactions in systems exhibiting strong, intermediate, or weak enhancement behavior. It is the examination and understanding of the topological details of the ground-state and phase diagrams of the model that allow the formulation of these criteria. The theoretically obtained criteria are supported by precise numerical calculations (transfer-matrix with strip width six) of adsorption isotherms for a three-state lattice-gas model with nearest-neighbor interactions on a triangular lattice. The applicability of this theoretical framework is illustrated by an analysis of experimental adsorption isotherms for the electrochemical adsorption of naphthalene on copper and n-decylamine on nickel, previously obtained by Bockris et al. As suggested by Damaskin et al. we attribute the potential dependence of the organic coverage to the influence of coadsorbed hydrogen. We find that nonlinear least-squares fits of numerical lattice-gas isotherms to the experimental data produce good agreement between the experimental and numerical adsorption isotherms, as well as effective lattice-gas interaction energies consistent with independent estimates from the literature.