Nanocrystallites, adsorption, surface tension, and Wulff rule

Artikel i vetenskaplig tidskrift, 2021

Chemisorption on the surface of metal nanocrystallites (NCs) sometimes induces their reshaping. This interesting phenomenon was observed experimentally in various systems. Related theoretical studies imply that it can be described using the Wulff rule with the surface tension dependent on the coverage of the NC facets by adsorbate. There is, however, no agreement as to how the surface tension should be calculated in this case. Relying on the laws of statistical physics, I clarify the situation in this area in general and also in the framework of the mean-field approximation in three situations: (i) with adsorption-desorption equilibrium, (ii) with a fixed amount of adsorbate at a NC, and (iii) with a fixed amount of adsorbate at facets of a NC. Under these conditions, the surface tension is shown to be described by the same expressions.