期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2010
卷号：107
期号：6
页码：2391-2396
DOI：10.1073/pnas.0911349107
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：Oxygen vacancies on metal oxide surfaces have long been thought to play a key role in the surface chemistry. Such processes have been directly visualized in the case of the model photocatalyst surface TiO2(110) in reactions with water and molecular oxygen. These vacancies have been assumed to be neutral in calculations of the surface properties. However, by comparing experimental and simulated scanning tunneling microscopy images and spectra, we show that oxygen vacancies act as trapping centers and are negatively charged. We demonstrate that charging the defect significantly affects the reactivity by following the reaction of molecular oxygen with surface hydroxyl formed by water dissociation at the vacancies. Calculations with electronically charged hydroxyl favor a condensation reaction forming water and surface oxygen adatoms, in line with experimental observations. This contrasts with simulations using neutral hydroxyl where hydrogen peroxide is found to be the most stable product.
关键词：photocatalysis ; STM/STS ; titania ; water ; molecular oxygen
