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Oxygen (O2) adsorbed on metal oxides is important in catalytic oxidationreactions, chemical sensing, and photocatalysis. Strong adsorption requirestransfer of negative charge from oxygen vacancies (VOs) or dopants, forexample. With scanning tunneling microscopy, we observed, transformed, and, inconjunction with theory, identified the nature of O2 molecules on the (101)surface of anatase (titanium oxide, TiO2) doped with niobium. VOs resideexclusively in the bulk, but we pull them to the surface with a stronglynegatively charged scanning tunneling microscope tip. O2 adsorbed as superoxo(O2)- at fivefold-coordinated Ti sites was transformed to peroxo (O2)2- and,via reaction with a VO, placed into an anion surface lattice site as an (O2)Ospecies. This so-called bridging dimer also formed when O2 directly reactedwith VOs at or below the surface.

Reaction of O2 with Subsurface Oxygen Vacancies on TiO2 Anatase (101)