Understanding the effect of halide poisoning in CO oxidation over Au/TiO2

The effect of halide poisoning of Au/TiO2 catalysts in low temperature CO oxidation was investigated using bromide as the poison and a combination of X-ray absorption spectroscopy (XANES and EXAFS), quantitative CO adsorption, and catalytic measurements. It was found that halide prevented full reduction of cationic Au by displacing oxyhydroxy ligands and remaining bound to Au during low temperature reduction, causing a reduction in catalytic activity. On reduced Au samples, bromide (likely as NaBr molecule) was preferentially adsorbed on Au and not on TiO2, and suppressed both the adsorption of CO and the catalytic activity. At low Br contents, each adsorbed Br suppressed adsorption of three CO, suggesting that Br was adsorbed on three-fold sites but the effect decreased with increasing Br content possibly due to crowding of adsorbed Br. When 5–10% of the Au was bound to Br, the catalytic activity was completely blocked, although ∼35% of the original CO adsorption capacity remained. The data suggest that not all CO adsorption sites are catalytic active sites, and are consistent with the perimeter Au atoms at/near the particle-support interface (perimeter) being active sites.

Graphical abstractHalide suppresses CO adsorption and CO oxidation activity on Au/TiO2 catalysts differently; the data were consistent with the perimeter of Au atoms at/near the particle-support interface (perimeter) being active sites, whereas all surface Au can adsorb CO.Figure optionsDownload full-size imageDownload as PowerPoint slide