Spectroscopic identification and catalytic relevance of NH4+ intermediates in selective NOx reduction over Cu-SSZ-13 zeolites

Authors：Rizzotto, Valentina; Chen, Dongdong; Tabak, Bjorn Martin; Yang, Jia-Yue; Ye, Daiqi; Simon, Ulrich; Chen, Peirong^*

Source：Chemosphere, 2020, 250: 126272.

DOI：10.1016/j.chemosphere.2020.126272

• In situ DRIFTS
• Cu redox
• Nitrogen oxides
• Zeolite catalyst
• DFT calculation

Reduction of harmful nitrogen oxides (NOx) from diesel engine exhausts is one of the key challenges in environmental protection, and can be achieved by NH3-assisted selective catalytic reduction (NH3-SCR) using copper-exchanged chabazite zeolites (i.e. Cu-CHA, including Cu-SSZ-13 and Cu-SAPO-34) as catalysts. Understanding the redox chemistry of Cu-CHA in NH3-SCR catalysis is crucial for further improving the NOx reduction efficiency. Here, a series of Cu-SSZ-13 catalysts with different Cu ion exchange levels were prepared, thoroughly characterized by different techniques such as X-ray diffraction, diffuse reflectance ultraviolet-visible spectroscopy and temperature-programmed desorption using NH3 as a probe molecule, etc., and tested in NH3-SCR reactions under steady-state conditions. In situ studies by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), supplemented with densityfunctional theory calculations, provided solid evidence for the formation of ammonium ion (NH4+) intermediates resulting from the reduction of Cu2+ to Cu+ by co-adsorbed NH3 and NO molecules on CuSSZ-13. Catalytic relevance of the NH4(+) intermediates, as demonstrated by an increase of NO conversion over Cu-SSZ-13 pre-treated in NH3/NO atmosphere, can be attributed to the formation of closely coupled Cu+/NH4(-) pairs promoting the Cu- re-oxidation and, consequently, the overall NH3-SCR process. This study thus paves a new route for improving the NH3-SCR efficiency over Cu-CHA zeolite catalyst.

• Institution
  山东大学; 1