Chemistry of Oxygen Ionosorption on SnO₂ Surfaces

Abstract

Ionosorbed oxygen is the key player in reactions on metal-oxide surfaces. This is particularly evident for chemiresistive gas sensors, which operate by modulating the conductivity of active materials through the formation/removal of surface O-related acceptors. Strikingly though, the exact type of species behind the sensing response remains obscure even for the most common material systems. The paradigm for <i>ab initio</i> modeling to date has been centered around charge-neutral surface species, ignoring the fact that molecular adsorbates are required to ionize to induce the sensing response. Herein, we resolve this inconsistency by carrying out a careful analysis of all charged O-related species on three naturally occurring surfaces of SnO₂. We reveal that two types of surface acceptors can form spontaneously upon the adsorption of atmospheric oxygen: (i) superoxide O₂^- on the (110) and the (101) surfaces and (ii) doubly ionized O^2- on the (100) facet, with the previous experimental evidence pointing to the latter as the source of sensing response. This species has a unique geometry involving a large displacement of surface Sn, forcing it to attain the coordination resembling that of Sn²⁺ in SnO, which seems necessary to stabilize O^2- and activate metal-oxide surfaces for gas sensing.