Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu‐SSZ‐131. (12th September 2014)

• Record Type: Journal Article
• Authors: Paolucci, Christopher; Verma, Anuj A.; Bates, Shane A.; Kispersky, Vincent F.; Miller, Jeffrey T.; Gounder, Rajamani; Delgass, W. Nicholas; Ribeiro, Fabio H.; Schneider, William F.
• Is Part Of: Angewandte Chemie. Volume 126:Number 44(2014)
• Page Start: 12022
• Page End: 12027
• Publication Date: 2014-09-12
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201407030
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Operando X‐ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu‐exchanged SSZ‐13. Catalysts prepared to contain only isolated, exchanged Cu^II ions evidence both Cu^II and Cu^I ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH₃ together are necessary for Cu^II reduction to Cu^I. DFT calculations show that NO‐assisted NH₃ dissociation is both energetically favorable and accounts for the observed Cu^II reduction. The calculations predict in situ generation of Brønsted sites proximal to Cu^I upon reduction, which we quantify in separate titration experiments. Both NO and O₂ are necessary for oxidation of Cu^I to Cu^II, which DFT suggests to occur by a NO₂ intermediate. Reaction of Cu‐bound NO₂ with proximal NH₄⁺ completes the catalytic cycle. N₂ is produced in both reduction and oxidation half‐cycles.</p> </abstract>