Environmentally dependent stability of low-index hematite surfaces

Nanoparticulate hematite is a promising material for catalytic and photoelectrochemical applications, where the surfaces are engineered to improve efficiency in different chemical environments. In the presence of water, the surfaces are typically passivated by hydroxyl groups, which modify the surface stability and reactivity. We use density functional theory and first principles thermodynamics to investigate the low-index surfaces (0. 0. 1), (1. 0. 1), and (1. 0. 4) in hydrous environments. For each of the surfaces, we build various hydroxylation configurations and compare their thermodynamic stability under different environmental conditions (temperature, humidity, and supersaturation of oxygen). The results enable us to construct surface phase diagrams, which provide guidance to the selection of surface structures, and the control of environmental conditions for specific applications.