Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 53, Issue 44, Pages 11828-11833Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201407030
Keywords
density functional calculations; heterogeneous catalysis; nitrogen oxides; operando spectroscopy; zeolites
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Funding
- U.S. Department of Energy (DoE) [DE-EE0003977]
- National Science Foundation GOALI [1258715-CBET]
- U.S. DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences [DE-AC0-06CH11357]
- Sachem, Inc [SSZ-13]
- Center for Research Computing at Notre Dame
- Directorate For Engineering
- Div Of Chem, Bioeng, Env, & Transp Sys [1258690] Funding Source: National Science Foundation
- Div Of Chem, Bioeng, Env, & Transp Sys
- Directorate For Engineering [1258715, 1258717] Funding Source: National Science Foundation
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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 Bronsted sites proximal to Cu-I upon reduction, which we quantify in separate titration experiments. Both NO and O-2 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. N-2 is produced in both reduction and oxidation half-cycles.
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