Carbonylation and Decarbonylation of γ-Al2O3-Supported Hexarhodium Clusters: Characterization by Infrared, 13C NMR, and Extended X-ray Absorption Fine Structure Spectroscopies
| Autor: | and Brian L. Phillips, Bruce C. Gates, Oleg S. Alexeev, Ghansham Panjabi |
|---|---|
| Rok vydání: | 2003 |
| Předmět: |
Extended X-ray absorption fine structure
Infrared Chemistry Decarbonylation Analytical chemistry chemistry.chemical_element Surfaces and Interfaces Carbon-13 NMR Condensed Matter Physics Rhodium Crystallography Electrochemistry General Materials Science Absorption (chemistry) Spectroscopy Carbonylation |
| Zdroj: | Langmuir. 19:9494-9503 |
| ISSN: | 1520-5827 0743-7463 |
| DOI: | 10.1021/la0348970 |
| Popis: | Rh6(CO)16 adsorbed on γ-Al2O3 that had been calcined at 400 °C was decarbonylated in steps by treatment in He at increasing temperatures. The metal frame in the supported clusters remained largely intact during the decarbonylation process as evidenced by extended X-ray absorption fine structure (EXAFS) spectroscopy. The face-bridging CO ligands were removed first when the temperature was raised to 100 °C and held for 2 h, as shown by infrared and 13C NMR data. Treatment in He at 300 °C led to complete removal of the carbonyl ligands and the formation of supported rhodium clusters with structures modeled on the basis of EXAFS data as Rh6 (along with some other species inferred to be cationic rhodium). These clusters were stable in He at temperatures as high as 400 °C. The infrared and 13C NMR data show that when the fully decarbonylated Rh6 clusters were exposed to CO at 25−200 °C, they were partially recarbonylated. Subsequent treatment of the partially recarbonylated clusters in He at 300 °C again led to... |
| Databáze: | OpenAIRE |
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