Amorphous SiO2 surface models: energetics of the dehydroxylation process, strain, ab initio atomistic thermodynamics and IR spectroscopic signatures

In this contribution, realistic amorphous SiO2 models of 2.1 × 2.1 nm with silanol densities ranging 1.1–7.2 OH per nm2 are obtained by means of ab initio calculations via the dehydroxylation of a fully hydroxylated silica surface. The dehydroxyation process is considered to take place via direct condensation of adjacent silanol groups and silica migration steps. The latter reconstructions are needed in order to obtain highly dehydroxylated silica surfaces with favorable energetics and without the formation of defects. The obtained surface phase diagram of different silica models as a function of temperature and PH2O is able to correctly describe the silanol density under different conditions, and the IR spectroscopic signatures of the silanols are in qualitative agreement with the experiment. The amorphous silica models presented here have a high degree of heterogeneity as found from the big variability obtained in the energetics of the dehydroxylation steps. It was also found that the resulting average Si–O distance of the newly formed siloxane bridges serves as a descriptor of the strain introduced in the silica surface. All these factors can be crucial in order to simulate the activity of catalysts grafted onto silica with different silanol densities, especially the one containing ca. 1 OH per nm2, which can serve as a model for the SiO2 surface pretreated under high vacuum and at 700 °C.