RESUMEN
Gold supported on ceria-zirconia is one of the most active low temperature water-gas shift catalysts reported to date but rapid deactivation occurs under reaction conditions. In this study, ceria-titania was evaluated as an alternative catalyst support. Materials of different Ce:Ti compositions were synthesized using a sol-gel methodology and gold was supported onto these using a deposition-precipitation method. They were then investigated as catalysts for the low-temperature water-gas shift reaction. Au/Ce0.2Ti0.8O2 exhibited superior activity and stability to a highly active, previously reported gold catalyst supported on ceria-zirconia. High activity and stability was found to be related to the support comprising a high number of oxygen defect sites and a high specific surface area. These properties were conducive to forming a highly active catalyst with well-dispersed Au species.
RESUMEN
Highly active and stable bimetallic Au-Pd catalysts have been extensively studied for several liquid-phase oxidation reactions in recent years, but there are far fewer reports on the use of these catalysts for low-temperature gas-phase reactions. Here we initially established the presence of a synergistic effect in a range of bimetallic Au-Pd/CeZrO4 catalysts, by measuring their activity for selective oxidation of benzyl alcohol. The catalysts were then evaluated for low-temperature WGS, CO oxidation, and formic acid decomposition, all of which are believed to be mechanistically related. A strong anti-synergy between Au and Pd was observed for these reactions, whereby the introduction of Pd to a monometallic Au catalyst resulted in a significant decrease in catalytic activity. Furthermore, monometallic Pd was more active than Pd-rich bimetallic catalysts. The nature of the anti-synergy was probed by several ex situ techniques, which all indicated a growth in metal nanoparticle size with Pd addition. However, the most definitive information was provided by in situ CO-DRIFTS, in which CO adsorption associated with interfacial sites was found to vary with the molar ratio of the metals and could be correlated with the catalytic activity of each reaction. As a similar correlation was observed between activity and the presence of Au0* (as detected by XPS), it is proposed that peripheral Au0* species form part of the active centers in the most active catalysts for the three gas-phase reactions. In contrast, the active sites for the selective oxidation of benzyl alcohol are generally thought to be electronically modified gold atoms at the surface of the nanoparticles.