Analysis of NH -TPD Profiles for CuSSZ-13 SCR Catalyst of Controlled Al Distribution - Complexity Resolved by First Principles Thermodynamics of NH Desorption, IR and EPR Insight into Cu Speciation*.

NH temperature-programmed desorption (NH -TPD) is frequently used for probing the nature of the active sites in CuSSZ-13 zeolite for selective catalytic reduction (SCR) of NO . Herein, we propose an interpretation of NH -TPD results, which takes into account the temperature-induced dynamics of NH interaction with the active centers. It is based on a comprehensive DFT/GGA+D and first-principles thermodynamic (FPT) modeling of NH adsorption on single Cu , Cu , [CuOH] centers, dimeric [Cu-O-Cu] , [Cu-O -Cu] species, segregated CuO nanocrystals and Brønsted acid sites (BAS). Theoretical TPD profiles are compared with the experimental data measured for samples of various Si/Al ratios and distribution of Al within the zeolite framework. Copper reduction, its relocation, followed by the intrazeolite olation/oxolation processes, which are concomitant with NH desorption, were revealed by electron paramagnetic resonance (EPR) and IR. DFT/FPT results show that the peaks in the desorption profiles cannot be assigned univocally to the particular Cu and BAS centers, since the observed low-, medium- and high-temperature desorption bands have contributions coming from several species, which dynamically change their speciation and redox states during NH -TPD experiment. Thus, a rigorous interpretation of the NH -TPD profiles of CuSSZ-13 in terms of the strength and concentration of the active centers of a particular type is problematic. Nonetheless, useful connections for molecular interpretation of TPD profiles can be established between the individual component peaks and the corresponding ensembles of the adsorption centers.