Activation of Molecular Oxygen and the Nature of the Active Oxygen Species for CO Oxidation on Oxide Supported Au Catalysts

作者：Widmann D; Behm R J^*

来源：Accounts of Chemical Research, 2014, 47(3): 740-749.

DOI：10.1021/ar400203e

Although highly dispersed Au catalysts with Au nanoparticles (NPs) of a few nanometers in diameter are well-known for their high catalytic activity for several oxidation and reduction reactions already at rather low temperatures for almost 30 years, central aspects of the reaction mechanism are still unresolved. While most studies focused on the active site, the active Au species, and the effect of the support material, the most crucial step during oxidation reactions, the activation of molecular oxygen and the nature of the resulting active oxygen species (O-act), received more attention just recently.
This is topic of this Account, which focuses on the formation, location, and nature of the O-act species present on metal oxide supported Au catalysts under typical reaction conditions, at room temperature and above. It is mainly based on quantitative temporal analysis of products (TAP) reactor measurements, which different from most spectroscopic techniques are able to detect and quantify these species even at the extremely low concentrations present under realistic reaction conditions. Different types of pulse experiments were performed, during which the highly dispersed, realistic powder catalysts are exposed to very low amounts of reactants, CO and/or O-2, in order to form and reactively remove O-act species and gain information on their formation, nature, and the active site for O-act formation.
Our investigations have shown that the active oxygen species for CO oxidation on Au/TiO2 for reaction at 80 degrees C and higher is a highly stable atomic species, which at 80 degrees C is formed only at the perimeter of the Au oxide interface and whose reactive removal by CO is activated, but not its formation. From these findings, it is concluded that surface lattice oxygen represents the O-act species for the CO oxidation. Accordingly, the CO oxidation proceeds via a Au-assisted Mars-van Krevelen mechanism, during which surface lattice oxygen close to the Au NPs is removed by reaction with CO, resulting in a partially reduced TiO2 surface, which is subsequently reoxidized by O-2. We demonstrate that this is the dominant reaction pathway for Au catalysts based on reducible metal oxides in general, at typical reaction temperatures, while for less active Au catalysts based on non reducible metal oxides, this reaction pathway is not possible and the remaining activity must arise from another pathway, most probably a Au-only mechanism. At lower reaction temperature, reactive removal of O-act becomes increasingly inhibited, leading to a change In the dominant reaction pathway.

• 出版日期2014-3-18