Water adsorbate phases on ZnO and impact of vapor pressure on the equilibrium shape of nanoparticles.

Abstract

ZnO nanoparticles are used as catalysts and have potential applications in gas-sensing and solar energy conversion. A fundamental understanding of the exposed crystal facets, their surface chemistry, and stability as a function of environmental conditions is essential for rational design and improvement of synthesis and properties. We study the stability of water adsorbate phases on the non-polar low-index (101¯0) and (112¯0) surfaces from low coverage to multilayers using ab initio thermodynamics. We show that phonon contributions and the entropies due to a 2D lattice gas at low coverage and multiple adsorbate configurations at higher coverage have an important impact on the stability range of water adsorbate phases in the (T,p) phase diagram. Based on this insight, we compute and analyze the possible growth mode of water films for pressures ranging from UHV via ambient conditions to high pressures and the impact of water adsorption on the equilibrium shape of nanoparticles in a humid environment. A 2D variant of the Wulff construction shows that the (101¯0) and (112¯0) surfaces coexist on 12-faceted prismatic ZnO nanoparticles in dry conditions, while in humid environment, the (101¯0) surface is selectively stabilized by water adsorption resulting in hexagonal prisms.