Nitric Oxide Reduction by Carbon Monoxide over Supported Hexaruthenium Cluster Catalyst. 1. The Active Site Structure That Depends on Supporting Metal Oxide and Catalytic Reaction Conditions

摘要

Ruthenium site structures supported on metal oxide surfaces were designed by reacting organometallic Ru cluster [Ru_6C(CO)_(16)]~(2-) or [Ru_6(CO)_(18)]~(2-) with various metal oxides, TiO_2, Al_2O_3, MgO, and SiO_2. The surface Ru site structure, formed under various catalyst preparation and reaction conditions, was investigated by the Ru K-edge extended X-ray absorption fine structure (EXAFS). Samples of [Ru_6C(CO)_(16)]~(2-)/TiO_2(anatase) and [Ru_6C(CO)_(16)]~(2-)/TiO_2(rutile) were found to retain the original Ru_6C framework when heated in the presence of NO (2.0 kPa) OR no (2.0 kPa) + CO (2.0 kPa) at 423 K, i.e., catalytic reaction conditions for NO decomposition. At 523 k, the Ru-R bonds of the Ru_6C framework were cleaved by the attack of NO. In contrast, the Ru site became spontaneously dispersed over TiO_2 (anatase). When being supported over TiO_2 (mesoporous), MgO, or Al_2O_3, the Ru_6C framework split into fragments in gaseous NO or NO + CO even at 423 K. The Ru_6 framework of [Ru_6(CO)_(16)]~(2-) was found to break easily into smaller ensembles in the presence of NO and/or CO at 423 K on support. Taking into consideration the realistic environments in which these catalysts will be used, we also examined the effect of water and oxygen. When water was introduced to the sample [Ru_6C(CO)_(16)]~(2-)/TiO_2(anatase) at 423 K, it did not have any effects on the stabilized Ru_6C framework structure. In the presence of oxygen gas, however, the Ru hexanuclear structure decomposed into isolate Ru cation bound to surface oxygen atoms of TiO_2 (anatase).