Destructive and Protective Effects of NH3 on the Low-Temperature Hydrothermal Stability of SAPO-34 and Cu-SAPO-34.

Abstract

The influences of gaseous, weakly adsorbed, and strongly adsorbed NH3 on the low-temperature (<100 °C) hydrothermal stability of SAPO-34 and Cu-SAPO-34 were investigated. NH3 temperature-programmed desorption (NH3-TPD), 1H magic angle spinning nuclear magnetic resonance (MAS NMR), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) were adopted to characterize the adsorption states of NH3 and H2O in SAPO-34, and the destruction of the SAPO-34 framework was revealed by direct and cross-polarization 29Si, 27Al, and 31P MAS NMR. Gaseous NH3 coadsorbed with H2O inside SAPO-34 micropores and induced the hydrolysis of framework P-O-Al and Si-O(H)-Al bonds. Weakly adsorbed NH3 was released during aging and played a similar negative role to gaseous NH3. When being combined with hydrolyzed Al species from the framework, active Cu ions transformed to inactive CuAl2O4-like species, leading to deactivation in low-temperature SCR of Cu-SAPO-34. Strongly adsorbed NH4+ via 200 °C preadsorption protected the framework integrity of SAPO-34 and the SCR activity of Cu-SAPO-34.