SnO₂ is the most widely used metal oxide gas-sensing material but a detailed understanding of its functioning is still lacking despite its relevance for applications. To gain new mechanistic insight into SnO₂ gas sensors under working conditions, we have developed an operando approach based on combined UV/Vis, Raman, and FTIR spectroscopy, allowing us for the first time to relate the sensor response to the concentration of oxygen vacancies in the metal oxide, the nature of the adsorbates, and the gas-phase composition. We demonstrate with the example of ethanol gas sensing that the sensor resistance is directly correlated with the number of surface oxygen vacancies and the presence of surface species, in particular, acetate and hydroxy groups. Our operando results enable an assessment of mechanistic models proposed in the literature to explain gas sensor operation. Owing to their fundamental nature, our findings are of direct relevance also for other metal oxide gas sensors.
