The H2O Effect on Cu Speciation in Cu-CHA-Catalysts for NH3-SCR Probed by NH3 Titration

The present work is focused on the effect of water on NH3 adsorption over Cu-CHA SCR catalysts. For this purpose, samples characterized by different SAR (SiO2/Al2O3) ratios and Cu loadings were studied under both dry and wet conditions. H2O adversely affects NH3 adsorption on Lewis acid sites (Cu ions) over all the tested catalysts, as indicated by the decreased NH3 desorption at low temperature during TPD. Interestingly, the NH3/Cu ratio, herein regarded as an index for the speciation of Cu cations, fell in the range of 3–4 (in the presence of gaseous NH3) or 1–2 (no gaseous NH3) in dry conditions, in line with the formation of different NH3-solvated Cu species (e.g., [CuII(NH3)4]2+ and [CuII(OH)(NH3)3]+ with gaseous NH3, [Z2CuII(NH3)2]2+ and [ZCuII(OH)(NH3)]+ without gaseous NH3). When H2O was fed to the system, on the contrary, the NH3/Cu ratio was always close to 3 (or 1), while the Brønsted acidity was slightly increased. These results are consistent both with competition between H2O and NH3 for adsorption on Lewis sites and with the hydrolysis of a fraction of Z2CuII species into ZCuIIOH.