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    Rate Controlling in Low-Temperature Standard NH3-SCR: Implications from Operando EPR Spectroscopy and Reaction Kinetics
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    • Yiqing Wu
      Yiqing Wu
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99354, United States
      More by Yiqing Wu
    • Yue Ma
      Yue Ma
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99354, United States
      More by Yue Ma
    • Yilin Wang
      Yilin Wang
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99354, United States
      More by Yilin Wang
    • Kenneth G. Rappé
      Kenneth G. Rappé
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99354, United States
      More by Kenneth G. Rappé
    • Nancy M. Washton
      Nancy M. Washton
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99354, United States
      More by Nancy M. Washton
      Orcidhttps://orcid.org/0000-0002-9643-6794
    • Yong Wang
      Yong Wang
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99354, United States
      Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, Washington 99163, United States
      More by Yong Wang
      Orcidhttps://orcid.org/0000-0002-8460-7410
    • Eric D. Walter*
      Eric D. Walter
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99354, United States
      *Email: [email protected]
      More by Eric D. Walter
      Orcidhttps://orcid.org/0000-0003-3644-5514
    • Feng Gao*
      Feng Gao
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99354, United States
      *Email: [email protected]
      More by Feng Gao
      Orcidhttps://orcid.org/0000-0002-8450-3419
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2022, 144, 22, 9734–9746
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    https://doi.org/10.1021/jacs.2c01933
    Published May 23, 2022
    Copyright © 2022 American Chemical Society
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    Abstract

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    A series of seven Cu/SSZ-13 catalysts with Si/Al = 6.7 are used to elucidate key rate-controlling factors during low-temperature standard ammonia-selective catalytic reduction (NH3-SCR), via a combination of SCR kinetics and operando electron paramagnetic resonance (EPR) spectroscopy. Strong Cu-loading-dependent kinetics, with Cu atomic efficiency increasing nearly by an order of magnitude, is found when per chabazite cage occupancy for Cu ion increases from ∼0.04 to ∼0.3. This is due mainly to the release of intercage Cu transfer constraints that facilitates the redox chemistry, as evidenced from detailed Arrhenius analysis. Operando EPR spectroscopy studies reveal strong connectivity between Cu-ion dynamics and SCR kinetics, based on which it is concluded that under low-temperature steady-state SCR, kinetically most relevant Cu species are those with the highest intercage mobility. Transient binuclear Cu species are mechanistically relevant species, but their splitting and cohabitation are indispensable for low-temperature kinetics.

    Copyright © 2022 American Chemical Society

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.2c01933.

    • Experimental details; BET surface areas and t-plot micropore volumes of the Cu/SSZ-13 catalysts; powder XRD patterns for the Cu/SSZ-13 catalysts; H2-TPR profiles for the hydrated Cu/SSZ-13 catalysts; amount of Cu applied versus the amount of Cu actually loaded on the catalysts in solution ion exchange; NOx conversion as a function of reaction temperature for standard SCR on the seven Cu/SSZ-13 catalysts measured at a GHSV of ∼4 × 105 h–1; magnified hyperfine region EPR spectra for hydrated Cu/SSZ-13 catalysts measured at 25 °C; degree of autoreduction of the Cu/SSZ-13 catalysts after a dehydration treatment at 350 °C for 30 min, measured by ratioing EPR signal areas prior to and after dehydration; operando EPR spectra acquired during steady-state standard SCR at temperatures from 100 to 350 °C at a GHSV of ∼4 × 105 h–1; and derivatives of the EPR spectra, emphasizing the presence of superhyperfine signals (PDF)

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    Cite this: J. Am. Chem. Soc. 2022, 144, 22, 9734–9746
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.2c01933
    Published May 23, 2022
    Copyright © 2022 American Chemical Society
    Request reuse permissions

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