CO oxidation studies over cluster-derived Au/TiO2 and AUROlite™ Au/TiO2 catalysts using DRIFTS

• Published in: Catalysis today 2013-06, Vol.208, p.72-81
• Main Authors: Gaur, Sarthak, Wu, Hongyi, Stanley, George G., More, Karren, Kumar, Challa S.S.R., Spivey, James J.
• Format: Article
• Language: English
• Subjects: Au catalysis; Au clusters; Au/TiO2; Catalysis; catalysts; catalytic activity; Chemistry; CO oxidation; DRIFTS; Exact sciences and technology; General and physical chemistry; oxidation; oxygen; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; thiols
• ISSN: 0920-5861; 1873-4308
• DOI: 10.1016/j.cattod.2012.10.029

[Display omitted] ► Demonstrated synthesis of atomically precise Au38 clusters. ► Showed catalytic effect of residual sulfur on Au/TiO2 catalysis of CO oxidation. ► Presented DRIFTS evidence for reaction mechanism. Thiol-ligated Au38(SC12H25)24 clusters were synthesized and supported on a microporous TiO2 support by incipient wetness impregnation. After a reductive pretreatment designed to remove the thiol ligands, the activity of catalyst was tested using CO oxidation in a fixed-bed reactor at 30 and 60°C. CO oxidation was also performed at similar conditions in an in situ FTIR (DRIFTS) cell to monitor the species that were formed during the reaction, and results were compared to commercially available Au/TiO2 catalyst. Our Au/TiO2 was less active than this commercial catalyst for CO oxidation, likely due to the presence of bidentate carbonate species. DRIFTS studies on the commercial catalyst showed strong peaks at 1718 and 1690cm−1 that are not present in our catalyst. We propose that these bands are due to bridging CO2 between AuTi and AuAu centers formed via direct oxygen atom transfer from the titania surface to AuCO. On the surface of our catalyst, however, a different reaction mechanism involving sulfur-mediated oxygen transfer at the Au-TiO2 interface has been proposed.