Reaction of O 2 with Subsurface Oxygen Vacancies on TiO 2 Anatase (101)

作者：Martin Setvín, Ulrich Aschauer, Philipp Scheiber, Ye-Fei Li, Weiyi Hou, Michael Schmid, Annabella Selloni, Ulrike Diebold · 发表于：Science · 年份：2013 · DOI：10.1126/science.1239879 · 被引用次数：565 · 研究领域：Catalytic Processes in Materials Science、Electronic and Structural Properties of Oxides、TiO2 Photocatalysis and Solar Cells

Oxygen (O2) adsorbed on metal oxides is important in catalytic oxidation reactions, chemical sensing, and photocatalysis. Strong adsorption requires transfer of negative charge from oxygen vacancies (V(O)s) or dopants, for example. With scanning tunneling microscopy, we observed, transformed, and, in conjunction with theory, identified the nature of O2 molecules on the (101) surface of anatase (titanium oxide, TiO2) doped with niobium. V(O)s reside exclusively in the bulk, but we pull them to the surface with a strongly negatively 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)O species. This so-called bridging dimer also formed when O2 directly reacted with V(O)s at or below the surface.