Understanding Solid-Gas Reaction Mechanisms by Operando Soft X-Ray Absorption Spectroscopy at Ambient Pressure

Ambient-pressure operando soft X-ray absorption spectroscopy (soft-XAS) was applied to study the reactivity of hydroxylated SnO₂ nanoparticles toward reducing gases. H₂ was first used as a test case, showing that the gas phase and surface states can be simultaneously probed: Soft-XAS at the O K-edge gains sensitivity toward the gas phase, while at the Sn M_4,5-edges, tin surface states are explicitly probed. Results obtained by flowing hydrocarbons (CH₄ and CH₃CHCH₂) unequivocally show that these gases react with surface hydroxyl groups to produce water without producing carbon oxides and release electrons that localize on Sn to eventually form SnO. The partially reduced SnO_2 -  layer at the surface of SnO₂ is readily reoxidized to SnO₂ by treating the sample with O₂ at mild temperatures (>200 °C), revealing the nature of "electron sponge" of tin oxide. The experiments, combined with DFT calculations, allowed devising of a mechanism for dissociative hydrocarbon adsorption on SnO₂, involving direct reduction of Sn sites at the surface via cleavage of C-H bonds and the formation of methoxy- and/or methyl-tin species at the surface.