Insights into Migration and Transformation of Cu Species during SO2 Poisoning and Hydrothermal Aging of Cu/SAPO-34 NH3-SCR Catalysts

Cu/SAPO-34 catalysts have been widely used for the reduction of NOx from diesel exhaust by ammonia-selective catalytic reduction (SCR). Sulfur poisoning remains a challenge for Cu/SAPO-34 catalysts in NH3-SCR, restricting its application. In this study, Cu/SAPO-34 samples containing a mixture of Cu species comprising isolated Cu2+ located in the 6MR, Cu(OH)(+) in 8MR, CuO clusters/nanoparticles, and Cu+ species were prepared. The Cu speciation during SO2 and hydrothermal aging of Cu/SAPO-34 SCR catalysts was subsequently studied. While hydrothermal aging had little effect on catalytic activity, the sulfur-aged sample exhibited deterioration in NH3-SCR activity over the temperature range of 100-575 degrees C. The breakage and collapse of the zeotype framework and chemical deactivation of the Cu/SAPO-34 catalyst after exposure to SO2 and H2O took place. A combination of X-ray photoelectron spectroscopy (XPS) and TGA-DT-DSC revealed the presence of ammonium bisulfate, copper bisulfate/sulfate, aluminum sulfate, and sulfuric acid after SO2 and H2O copoisoning under SCR conditions. Furthermore, Cu(OH)(+) tended to migrate to form isolated Cu2+ and Cu+, as well as agglomerate to form CuO particles. Density functional theory (DFT) calculations revealed that SO2 and O-2 could readily be absorbed by CuO particles to form stable copper bisulfate/sulfate species with the following order of preference: CuO > Cu+ > Cu2+ > Cu(OH)(+). In contrast, Cu(OH)(+) was less prone to be poisoned by easily releasing SO3 than other Cu species sites.