CO oxidation catalyzed by oxide-supported Au25(SR)18 nanoclusters and identification of perimeter sites as active centers.
In this work, we explore the catalytic application of atomically monodisperse, thiolate-protected Au(25)(SR)(18) (where R = CH(2)CH(2)Ph) nanoclusters supported on oxides for CO oxidation. The solution phase nanoclusters were directly deposited onto various oxide supports (including TiO(2), CeO(2), and Fe(2)O(3)), and the as-prepared catalysts were evaluated for the CO oxidation reaction in a fixed bed reactor. The supports exhibited a strong effect, and the Au(25)(SR)(18)/CeO(2) catalyst was found to be much more active than the others. Interestingly, O(2) pretreatment of the catalyst at 150 °C for 1.5 h significantly enhanced the catalytic activity. Since this pretreatment temperature is well below the thiolate desorption temperature (~200 °C), the thiolate ligands should remain on the Au(25) cluster surface, indicating that the CO oxidation reaction is catalyzed by intact Au(25)(SR)(18)/CeO(2). We further found that increasing the O(2) pretreatment temperature to 250 °C (above the thiolate desorption temperature) did not lead to any further increase in activity at all reaction temperatures from room temperature to 100 °C. These results are in striking contrast with the common thought that surface thiolates must be removed-as is often done in the literature work-before the catalyst can exert high catalytic activity. The 150 °C O(2)-pretreated Au(25)(SR)(18)/CeO(2) catalyst offers ~94% CO conversion at 80 °C and ~100% conversion at 100 °C. The effect of water vapor on the catalytic performance is also investigated. Our results imply that the perimeter sites of the interface of Au(25)(SR)(18)/CeO(2) should be the active centers. The intact structure of the Au(25)(SR)(18) catalyst in the CO oxidation process allows one to gain mechanistic insight into the catalytic reaction.
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Xiaotao
X
Nie
Huifeng
H
Qian
Qingjie
Q
Ge
Hengyong
H
Xu
Rongchao
R
Jin