Chemistry of Oxygen Ionosorption on SnO2 Surfaces

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 ab initio 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 O2- 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 O2- and activate metal-oxide surfaces for gas sensing.

Automated summary

The study investigated charged oxygen-related species on three naturally occurring surfaces of SnO2 and found that upon adsorption of atmospheric oxygen, superoxide O2- and doubly ionized O2- can spontaneously form, with the latter being identified as the source of sensing response. The doubly ionized O2- species induces a large displacement of surface Sn, resembling the coordination of Sn2+ in SnO, which is necessary for stabilizing O2- and activating metal-oxide surfaces for gas sensing.