Thiolate ligands as a double-edged sword for CO oxidation on CeO2-supported Au25(SR)18 nanoclusters
- ORNL
- University of Tennessee, Knoxville (UTK)
- Carnegie Mellon University (CMU)
The effect of thiolate ligands was explored on the catalysis of CeO2-rod supported Au25(SR)18 (SR = -SCH2-CH2-Ph) by using CO oxidation as a probe reaction. Reaction kinetic tests, in situ IR and X-ray absorption spectroscopy, and density functional theory (DFT) were employed to understand how the thiolate ligands affect the nature of active sites, activation of CO and O2, as well as the reaction mechanism and kinetics. The intact Au25(SR)18 on CeO2-rod is found not able to adsorb CO. Only when the thiolate ligands are partially removed, starting from the interface between Au25(SR)18 and CeO2 at temperatures of 423 K and above, can the adsorption of CO be observed by IR. DFT calculations suggest that CO adsorbs favorably on the exposed gold atoms. Accordingly, the CO oxidation light-off temperature shifts to lower temperature. Several types of Au sites are probed by IR of CO adsorption during the ligand removal process. The cationic Au sites (charged between 0 and +1) are found to play the major role for low temperature CO oxidation. Similar activation energy and reaction rate are found for CO oxidation on differently treated Au25(SR)18/CeO2-rod, suggesting a simple site-blocking effect of the thiolate ligands in Au nanoclusters catalysis. Isotopic labelling experiments clearly indicate that CO oxidation on Au25(SR)18/CeO2-rod proceeds predominantly via the redox mechanism where CeO2 activates O2 while CO is activated on the de-thiolated gold sites. These results points to a double-edged sword role played by the thiolate ligands on Au25 nanoclusters for CO oxidation.
- Research Organization:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
- Sponsoring Organization:
- USDOE Office of Science (SC)
- DOE Contract Number:
- DE-AC05-00OR22725
- OSTI ID:
- 1150347
- Journal Information:
- Journal of the American Chemical Society, Vol. 136, Issue 16; ISSN 0002--7863
- Country of Publication:
- United States
- Language:
- English
Similar Records
CO oxidation over ceria supported Au22 nanoclusters: Shape effect of the support
Diphosphine-Protected Au22 Nanoclusters on Oxide Supports Are Active for Gas-Phase Catalysis without Ligand Removal