In-situ DRIFTS measurements for the mechanistic study of NO oxidation over a commercial Cu-CHA catalyst

Ruggeri, Maria Pia; Nova, Isabella; Tronconi, Enrico; Pihl, Josh A.; Toops, Todd J.; Partridge, Jr., William P.

doi:10.1016/j.apcatb.2014.10.076

Title: In-situ DRIFTS measurements for the mechanistic study of NO oxidation over a commercial Cu-CHA catalyst

Journal Article · Mon Nov 03 00:00:00 EST 2014 · Applied Catalysis B: Environmental

DOI:https://doi.org/10.1016/j.apcatb.2014.10.076· OSTI ID:1207044

Ruggeri, Maria Pia ^[1]; Nova, Isabella ^[1]; Tronconi, Enrico ^[1]; Pihl, Josh A. ^[2]; Toops, Todd J. ^[2]; Partridge, Jr., William P. ^[2]

Politecnico di Milano, Milano (Italy)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

We report a mechanistic DRIFTS in-situ study of NO₂, NO + O₂ and NO adsorption on a commercial Cu-CHA catalyst for NH₃-SCR of NO_x. Both pre-reduced and pre-oxidized catalyst samples were investigated with the aim of clarifying mechanistic aspects of the NO oxidation to NO₂ as a preliminary step towards the study of the Standard SCR reaction mechanism at low temperatures. Nitrosonium cations (NO⁺, N formal oxidation state = +3) were identified as key surface intermediates in the process of NO (+2) oxidation to NO₂ (+4) and nitrates (+5). While NO⁺ and nitrates were formed simultaneously upon catalyst exposure to NO₂, nitrates evolved consecutively to NO⁺ when the catalyst was exposed to NO + O₂, suggesting that nitrite-like species, and not NO₂, are formed as the primary products of the NO oxidative activation over Cu-CHA. Upon catalyst exposure to NO only, i.e. in the absence of gaseous O₂, NO⁺ and then nitrates were formed on a pre-oxidized sample but not on a pre-reduced one, which demonstrates the red-ox nature of the NO oxidation mechanism. The negative effect of H₂O on NO⁺ and nitrates formation was also clearly established. Assuming Cu dimers as the active sites for NO oxidation to NO₂, we propose a mechanism which reconciles all the experimental observations. Specifically, we show that such a mechanism also explains the observed kinetic effects of H₂O, O₂ and NO₂ on the NO oxidation activity of the investigated Cu zeolite catalyst.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1207044

Alternate ID(s):: OSTI ID: 1249856

Journal Information:: Applied Catalysis B: Environmental, Vol. 166; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 117 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Cu-Chabazite catalyst
NO oxidation
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nitrates
nitrosonium ion

Title: In-situ DRIFTS measurements for the mechanistic study of NO oxidation over a commercial Cu-CHA catalyst

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