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Herein, we propose an interpretation of NH<jats:sub>3<\/jats:sub>\u2010TPD results, which takes into account the temperature\u2010induced dynamics of NH<jats:sub>3<\/jats:sub> interaction with the active centers. It is based on a comprehensive DFT\/GGA+D and first\u2010principles thermodynamic (FPT) modeling of NH<jats:sub>3<\/jats:sub> adsorption on single Cu<jats:sup>2+<\/jats:sup>, Cu<jats:sup>+<\/jats:sup>, [CuOH]<jats:sup>+<\/jats:sup> centers, dimeric [Cu\u2010O\u2010Cu]<jats:sup>2+<\/jats:sup>, [Cu\u2010O<jats:sub>2<\/jats:sub><jats:sup>2\u2212<\/jats:sup>\u2010Cu]<jats:sup>2<\/jats:sup> species, segregated CuO nanocrystals and Br\u00f8nsted 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<jats:sub>3<\/jats:sub> 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\u2010, medium\u2010 and high\u2010temperature desorption bands have contributions coming from several species, which dynamically change their speciation and redox states during NH<jats:sub>3<\/jats:sub>\u2010TPD experiment. Thus, a rigorous interpretation of the NH<jats:sub>3<\/jats:sub>\u2010TPD profiles of CuSSZ\u201013 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.<\/jats:p>","DOI":"10.1002\/chem.202102790","type":"journal-article","created":{"date-parts":[[2021,11,9]],"date-time":"2021-11-09T06:29:37Z","timestamp":1636439377000},"page":"17159-17180","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":52,"title":["Analysis of NH<sub>3<\/sub>\u2010TPD Profiles for CuSSZ\u201013 SCR Catalyst of Controlled Al Distribution \u2013 Complexity Resolved by First Principles Thermodynamics of NH<sub>3<\/sub> Desorption, IR and EPR Insight into Cu Speciation**"],"prefix":"10.1002","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7818-7210","authenticated-orcid":false,"given":"Bartosz","family":"Mozgawa","sequence":"first","affiliation":[{"name":"Faculty of Chemistry Jagiellonian University  ul. 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Gronostajowa 2 30-387 Krakow Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4071-8610","authenticated-orcid":false,"given":"Edyta","family":"Tabor","sequence":"additional","affiliation":[{"name":"J. Heyrovsk\u00fd Institute of Physical Chemistry Czech Academic Sciences  Dolej\u0161kova 3 Prague 18223 Czech Republic"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3242-6535","authenticated-orcid":false,"given":"Kinga","family":"Mlekodaj","sequence":"additional","affiliation":[{"name":"J. Heyrovsk\u00fd Institute of Physical Chemistry Czech Academic Sciences  Dolej\u0161kova 3 Prague 18223 Czech Republic"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3697-8815","authenticated-orcid":false,"given":"Ji\u0159\u00ed","family":"D\u011bde\u010dek","sequence":"additional","affiliation":[{"name":"J. 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