Promotional mechanism of enhanced denitration activity with Cu modification in a Ce/TiO₂-ZrO₂ catalyst for a low temperature NH₃-SCR system

This study aims to investigate the enhanced low temperature denitration activity and promotional mechanism of a cerium-based catalyst through copper modification. In this paper, copper and cerium oxides were supported on TiO2-ZrO2 by an impregnation method, their catalytic activity tests of selective catalytic reduction (SCR) of NO with NH3 were carried out and their physicochemical properties were characterized. The CuCe/TiO2-ZrO2 catalyst shows obviously enhanced NH3-SCR activity at low temperature (<300 degrees C), which is associated with the well dispersed active ingredients and the synergistic effect between copper and cerium species (Cu2+ + Ce3+ <-> Cu+ + Ce4+), and the increased ratios of surface chemisorbed oxygen and Cu+/Cu2+ lead to the enhanced low-temperature SCR activity. The denitration reaction mechanism over the CuCe/TiO2-ZrO2 catalyst was investigated by in situ DRIFTS and DFT studies. Results illustrate that the NH3 is inclined to adsorb on the Cu acidic sites (Lewis acid sites), and the NH2 and NH2NO species are the key intermediates in the low-temperature NH3-SCR process, which can explain the promotional effect of Cu modification on denitration activity of Ce/TiO2-ZrO2 at the molecular level. Finally, we have reasonably concluded a NH3-SCR catalytic cycle involving the Eley-Rideal mechanism and Langmuir-Hinshelwood mechanism, and the former mechanism dominates in the NH3-SCR reaction.