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Title: Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13

Abstract

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 CuII ions evidence both CuII and CuI ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for CuII reduction to CuI. DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed CuII reduction. The calculations predict in situ generation of Brønsted sites proximal to CuI upon reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of CuI to CuII, 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.

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1222131
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Angewandte Chemie International Edition, 53(44):11828–11833
Additional Journal Information:
Journal Name: Angewandte Chemie International Edition, 53(44):11828–11833
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Paolucci, Christopher, Verma, Anuj A., Bates, Shane A., Kispersky, Vincent F., Miller, Jeffrey T., Gounder, Rajmani, Delgass, Nick, Ribeiro, Fabio, and Schneider, William F. Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13. United States: N. p., 2014. Web. doi:10.1002/anie.201407030.
Paolucci, Christopher, Verma, Anuj A., Bates, Shane A., Kispersky, Vincent F., Miller, Jeffrey T., Gounder, Rajmani, Delgass, Nick, Ribeiro, Fabio, & Schneider, William F. Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13. United States. https://doi.org/10.1002/anie.201407030
Paolucci, Christopher, Verma, Anuj A., Bates, Shane A., Kispersky, Vincent F., Miller, Jeffrey T., Gounder, Rajmani, Delgass, Nick, Ribeiro, Fabio, and Schneider, William F. 2014. "Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13". United States. https://doi.org/10.1002/anie.201407030.
@article{osti_1222131,
title = {Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13},
author = {Paolucci, Christopher and Verma, Anuj A. and Bates, Shane A. and Kispersky, Vincent F. and Miller, Jeffrey T. and Gounder, Rajmani and Delgass, Nick and Ribeiro, Fabio and Schneider, William F.},
abstractNote = {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 CuII ions evidence both CuII and CuI ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for CuII reduction to CuI. DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed CuII reduction. The calculations predict in situ generation of Brønsted sites proximal to CuI upon reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of CuI to CuII, 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.},
doi = {10.1002/anie.201407030},
url = {https://www.osti.gov/biblio/1222131}, journal = {Angewandte Chemie International Edition, 53(44):11828–11833},
number = ,
volume = ,
place = {United States},
year = {Mon Oct 27 00:00:00 EDT 2014},
month = {Mon Oct 27 00:00:00 EDT 2014}
}