Resolving the adsorption of molecular O2 on the rutile TiO2 (110) surface by noncontact atomic force microscopy

Proceedings of the National Academy of Sciences of the United States of America
Igor SokolovićMartin Setvín

Abstract

Interaction of molecular oxygen with semiconducting oxide surfaces plays a key role in many technologies. The topic is difficult to approach both by experiment and in theory, mainly due to multiple stable charge states, adsorption configurations, and reaction channels of adsorbed oxygen species. Here we use a combination of noncontact atomic force microscopy (AFM) and density functional theory (DFT) to resolve [Formula: see text] adsorption on the rutile [Formula: see text](110) surface, which presents a longstanding challenge in the surface chemistry of metal oxides. We show that chemically inert AFM tips terminated by an oxygen adatom provide excellent resolution of both the adsorbed species and the oxygen sublattice of the substrate. Adsorbed [Formula: see text] molecules can accept either one or two electron polarons from the surface, forming superoxo or peroxo species. The peroxo state is energetically preferred under any conditions relevant for applications. The possibility of nonintrusive imaging allows us to explain behavior related to electron/hole injection from the tip, interaction with UV light, and the effect of thermal annealing.

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Citations

Apr 30, 2021·Nature·Margareta WagnerUlrike Diebold
Oct 9, 2021·Science Advances·Hyeuk Jin HanJudy J Cha

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