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

Abstract

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,more »« less

Authors:

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)

Publication Date:: Mon Nov 03 00:00:00 EST 2014

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

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

OSTI Identifier:: 1207044

Alternate Identifier(s):: OSTI ID: 1249856

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Applied Catalysis B: Environmental

Additional Journal Information:: Journal Volume: 166; Journal ID: ISSN 0926-3373

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cu-Chabazite catalyst; NO oxidation; NH₃ SCR mechanism; nitrates; nitrosonium ion

Citation Formats


                    Ruggeri, Maria Pia, Nova, Isabella, Tronconi, Enrico, Pihl, Josh A., Toops, Todd J., and Partridge, Jr., William P. In-situ DRIFTS measurements for the mechanistic study of NO oxidation over a commercial Cu-CHA catalyst.  United States: N. p., 2014. 
Web.  doi:10.1016/j.apcatb.2014.10.076.

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                    Ruggeri, Maria Pia, Nova, Isabella, Tronconi, Enrico, Pihl, Josh A., Toops, Todd J., & Partridge, Jr., William P. In-situ DRIFTS measurements for the mechanistic study of NO oxidation over a commercial Cu-CHA catalyst.  United States.  https://doi.org/10.1016/j.apcatb.2014.10.076

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                    Ruggeri, Maria Pia, Nova, Isabella, Tronconi, Enrico, Pihl, Josh A., Toops, Todd J., and Partridge, Jr., William P. Mon .  
"In-situ DRIFTS measurements for the mechanistic study of NO oxidation over a commercial Cu-CHA catalyst".  United States.  https://doi.org/10.1016/j.apcatb.2014.10.076.  https://www.osti.gov/servlets/purl/1207044.

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@article{osti_1207044,

  title        = {In-situ DRIFTS measurements for the mechanistic study of NO oxidation over a commercial Cu-CHA catalyst},

  author       = {Ruggeri, Maria Pia and Nova, Isabella and Tronconi, Enrico and Pihl, Josh A. and Toops, Todd J. and Partridge, Jr., William P.},

  abstractNote = {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 NOx. 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.},

  doi          = {10.1016/j.apcatb.2014.10.076},

  journal      = {Applied Catalysis B: Environmental},

  number       = ,

  volume       = 166,

  place        = {United States},

  year         = {Mon Nov 03 00:00:00 EST 2014},

  month        = {Mon Nov 03 00:00:00 EST 2014}

}

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

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FTIR in situ mechanistic study of the NH3NO/NO2 “Fast SCR” reaction over a commercial Fe-ZSM-5 catalyst journal, April 2012

Experimental and kinetic modeling study of NO oxidation: Comparison of Fe and Cu-zeolite catalysts journal, April 2012

A comparative study of “standard”, “fast” and “NO2” SCR reactions over Fe/zeolite catalyst journal, December 2010

Detailed kinetic modeling of NH3 SCR over Cu-ZSM-5 journal, October 2009

Experimental Study of the NO Oxidation to NO2 Over Metal Promoted Zeolites Aimed at the Identification of the Standard SCR Rate Determining Step journal, February 2013

Thermal durability of Cu-CHA NH3-SCR catalysts for diesel NOx reduction journal, April 2012

Quantification of the in situ DRIFT spectra of Pt/K/γ-A12O3 NOx adsorber catalysts journal, June 2005

New sulfur adsorbents derived from layered double hydroxides journal, August 2008

Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NOx with NH3 journal, October 2010

Fourier Transform Infrared Spectroscopy Study of the Nature and Reactivity of NO x Compounds Formed after Coadsorption of NO and O 2 on Cu/ZrO 2 journal, April 2003

Co-adsorption of propene and nitrogen oxides on Cu-ZSM-5: An FTIR study journal, December 1995

A simultaneous infrared and kinetic study of the reduction of nitric oxide by carbon monoxide over copper oxide journal, October 1973

Use of overtones and combination modes for the identification of surface NOx anionic species by IR spectroscopy journal, January 2000

The Adsorption of NO and Reaction of NO with O2on H-, NaH-, CuH-, and Cu-ZSM-5: Anin SituFTIR Investigation journal, November 1996

Nitrosyl complexes on Co–ZSM-5: an FTIR spectroscopic study journal, March 2003

A Common Intermediate for N 2 Formation in Enzymes and Zeolites: Side-On Cu-Nitrosyl Complexes journal, August 2013

Characterization of Cu-SSZ-13 NH3 SCR catalysts: an in situ FTIR study journal, January 2013

Two different cationic positions in Cu-SSZ-13? journal, January 2012

Copper Coordination in Cu-SSZ-13 and Cu-SSZ-16 Investigated by Variable-Temperature XRD journal, December 2009

A comparative study of the NH3-SCR reactions over a Cu-zeolite and a Fe-zeolite catalyst journal, June 2010

Effect of water on the reduction of NOx with propane on Fe‐ZSM‐5. An FTIR mechanistic study journal, January 1999

Integrated operando X-ray absorption and DFT characterization of Cu–SSZ-13 exchange sites during the selective catalytic reduction of NOx with NH3 journal, April 2012

Study of copper(II) location and adsorbate interaction in CuH-SAPO-34 molecular sieve by electron spin resonance and electron spin echo modulation spectroscopies journal, March 1992

Structure refinement, electron microscopy, and solid-state magic angle spinning nuclear magnetic resonance characterization of AlPO4-52: An aluminophosphate with a large cage journal, June 1995

Rietveld structure refinement of NH4-exchanged natural chabazite [Rietveld structure refinement of NH4-exchanged natural chabazite] journal, July 2006

Mechanistic Cause of Hydrocarbon Specificity over Cu/ZSM-5 and Co/ZSM-5 Catalysts in the Selective Catalytic Reduction of NOx journal, January 1996

Structure–activity relationships in NH3-SCR over Cu-SSZ-13 as probed by reaction kinetics and EPR studies journal, April 2013

Characterization of copper species over Cu/SAPO-34 in selective catalytic reduction of NO x with ammonia: Relationships between active Cu sites and de-NO x performance at low temperature journal, January 2013

Identification of the active Cu site in standard selective catalytic reduction with ammonia on Cu-SSZ-13 journal, April 2014

Adsorption and reactivity of nitrogen oxides (NO2, NO, N2O) on Fe–zeolites journal, June 2009

Influence of the preparation method on the properties of Fe-ZSM-5 for the selective catalytic reduction of NO by n-decane journal, October 2005

NO2 adsorption on Fe- and Cu-zeolite catalysts: The effect of the catalyst red–ox state journal, January 2012

Characterization of Cu-exchanged SSZ-13: a comparative FTIR, UV-Vis, and EPR study with Cu-ZSM-5 and Cu-β with similar Si/Al and Cu/Al ratios journal, January 2013

Nature of active species in copper-based catalysts and their chemistry of transformation of nitrogen oxides journal, November 1995

Identification of nitrites/HONO as primary products of NO oxidation over Fe-ZSM-5 and their role in the Standard SCR mechanism: A chemical trapping study journal, March 2014

Identification of active sites and reaction mechanism on low-temperature SCR activity over Cu-SSZ-13 catalysts prepared by different methods journal, January 2016

The dynamic nature of Cu sites in Cu-SSZ-13 and the origin of the seagull NO x conversion profile during NH 3 -SCR journal, January 2019

Catalyst systems for selective catalytic reduction + NO x trapping: from fundamental understanding of the standard SCR reaction to practical applications for lean exhaust after-treatment journal, January 2019

Evidence of Mixed‐Ligand Complexes in Cu−CHA by Reaction of Cu Nitrates with NO/NH 3 at Low Temperature journal, June 2019

Catalytic performance of Co–Fe mixed oxide for NH 3 -SCR reaction and the promotional role of cobalt journal, January 2016

Investigating the Low Temperature Formation of Cu II ‐(N,O) Species on Cu‐CHA Zeolites for the Selective Catalytic Reduction of NO x journal, June 2018

Temperature-dependent dynamics of NH 3 -derived Cu species in the Cu-CHA SCR catalyst journal, January 2019

Promotional effect of the TiO 2 (001) facet in the selective catalytic reduction of NO with NH 3 : in situ DRIFTS and DFT studies journal, January 2016

Catalytic oxidation of NO over MnO 2 with different crystal structures journal, January 2016

The correlation between surface defects and the behavior of hydrogen adsorption over ZnO under UV light irradiation journal, January 2018

Quantitative determination of the Cu species, acid sites and NH 3 -SCR mechanism on Cu-SSZ-13 and H-SSZ-13 at low temperatures journal, January 2020

The dynamic nature of Cu sites in Cu-SSZ-13 and the origin of the seagull NOx conversion profile during NH3-SCR null, January 2019

A “Nitrate Route” for the low temperature “Fast SCR” reaction over a V ₂ O ₅ –WO ₃ /TiO ₂ commercial catalyst
journal, January 2004

NH3–NO/NO2 chemistry over V-based catalysts and its role in the mechanism of the Fast SCR reaction
journal, April 2006

NH3-NO/NO2 SCR for diesel exhausts after treatment: mechanism and modelling of a catalytic converter
journal, May 2007

Enhanced Reoxidation of Vanadia by NO2 in the Fast SCR Reaction
journal, July 2002

The chemistry of the NO/NO2–NH3 “fast” SCR reaction over Fe-ZSM5 investigated by transient reaction analysis
journal, June 2008

Ammonia blocking of the “Fast SCR” reactivity over a commercial Fe-zeolite catalyst for Diesel exhaust aftertreatment
journal, July 2009

The role of NO in the mechanism of reduction with ammonia over a BaNa?Y catalyst
journal, April 2005

FTIR in situ mechanistic study of the NH3NO/NO2 “Fast SCR” reaction over a commercial Fe-ZSM-5 catalyst
journal, April 2012

Experimental and kinetic modeling study of NO oxidation: Comparison of Fe and Cu-zeolite catalysts
journal, April 2012

A comparative study of “standard”, “fast” and “NO2” SCR reactions over Fe/zeolite catalyst
journal, December 2010

Detailed kinetic modeling of NH3 SCR over Cu-ZSM-5
journal, October 2009

Experimental Study of the NO Oxidation to NO2 Over Metal Promoted Zeolites Aimed at the Identification of the Standard SCR Rate Determining Step
journal, February 2013

Thermal durability of Cu-CHA NH3-SCR catalysts for diesel NOx reduction
journal, April 2012

Quantification of the in situ DRIFT spectra of Pt/K/γ-A12O3 NOx adsorber catalysts
journal, June 2005

New sulfur adsorbents derived from layered double hydroxides
journal, August 2008

Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NOx with NH3
journal, October 2010

Fourier Transform Infrared Spectroscopy Study of the Nature and Reactivity of NO _x Compounds Formed after Coadsorption of NO and O ₂ on Cu/ZrO ₂
journal, April 2003

Co-adsorption of propene and nitrogen oxides on Cu-ZSM-5: An FTIR study
journal, December 1995

A simultaneous infrared and kinetic study of the reduction of nitric oxide by carbon monoxide over copper oxide
journal, October 1973

Use of overtones and combination modes for the identification of surface NO_x anionic species by IR spectroscopy
journal, January 2000

The Adsorption of NO and Reaction of NO with O2on H-, NaH-, CuH-, and Cu-ZSM-5: Anin SituFTIR Investigation
journal, November 1996

Nitrosyl complexes on Co–ZSM-5: an FTIR spectroscopic study
journal, March 2003

A Common Intermediate for N ₂ Formation in Enzymes and Zeolites: Side-On Cu-Nitrosyl Complexes
journal, August 2013

Characterization of Cu-SSZ-13 NH3 SCR catalysts: an in situ FTIR study
journal, January 2013

Two different cationic positions in Cu-SSZ-13?
journal, January 2012

Copper Coordination in Cu-SSZ-13 and Cu-SSZ-16 Investigated by Variable-Temperature XRD
journal, December 2009

A comparative study of the NH3-SCR reactions over a Cu-zeolite and a Fe-zeolite catalyst
journal, June 2010

Effect of water on the reduction of NOx with propane on Fe‐ZSM‐5. An FTIR mechanistic study
journal, January 1999

Integrated operando X-ray absorption and DFT characterization of Cu–SSZ-13 exchange sites during the selective catalytic reduction of NOx with NH3
journal, April 2012

Study of copper(II) location and adsorbate interaction in CuH-SAPO-34 molecular sieve by electron spin resonance and electron spin echo modulation spectroscopies
journal, March 1992

Structure refinement, electron microscopy, and solid-state magic angle spinning nuclear magnetic resonance characterization of AlPO4-52: An aluminophosphate with a large cage
journal, June 1995

Rietveld structure refinement of NH4-exchanged natural chabazite [Rietveld structure refinement of NH4-exchanged natural chabazite]
journal, July 2006

Mechanistic Cause of Hydrocarbon Specificity over Cu/ZSM-5 and Co/ZSM-5 Catalysts in the Selective Catalytic Reduction of NOx
journal, January 1996

Structure–activity relationships in NH3-SCR over Cu-SSZ-13 as probed by reaction kinetics and EPR studies
journal, April 2013

Characterization of copper species over Cu/SAPO-34 in selective catalytic reduction of NO x with ammonia: Relationships between active Cu sites and de-NO x performance at low temperature
journal, January 2013

Identification of the active Cu site in standard selective catalytic reduction with ammonia on Cu-SSZ-13
journal, April 2014

Adsorption and reactivity of nitrogen oxides (NO2, NO, N2O) on Fe–zeolites
journal, June 2009

Influence of the preparation method on the properties of Fe-ZSM-5 for the selective catalytic reduction of NO by n-decane
journal, October 2005

NO2 adsorption on Fe- and Cu-zeolite catalysts: The effect of the catalyst red–ox state
journal, January 2012

Characterization of Cu-exchanged SSZ-13: a comparative FTIR, UV-Vis, and EPR study with Cu-ZSM-5 and Cu-β with similar Si/Al and Cu/Al ratios
journal, January 2013

Nature of active species in copper-based catalysts and their chemistry of transformation of nitrogen oxides
journal, November 1995

Identification of nitrites/HONO as primary products of NO oxidation over Fe-ZSM-5 and their role in the Standard SCR mechanism: A chemical trapping study
journal, March 2014

Identification of active sites and reaction mechanism on low-temperature SCR activity over Cu-SSZ-13 catalysts prepared by different methods
journal, January 2016

The dynamic nature of Cu sites in Cu-SSZ-13 and the origin of the seagull NO _x conversion profile during NH ₃ -SCR
journal, January 2019

Catalyst systems for selective catalytic reduction + NO x trapping: from fundamental understanding of the standard SCR reaction to practical applications for lean exhaust after-treatment
journal, January 2019

Evidence of Mixed‐Ligand Complexes in Cu−CHA by Reaction of Cu Nitrates with NO/NH ₃ at Low Temperature
journal, June 2019

Catalytic performance of Co–Fe mixed oxide for NH ₃ -SCR reaction and the promotional role of cobalt
journal, January 2016

Investigating the Low Temperature Formation of Cu II ‐(N,O) Species on Cu‐CHA Zeolites for the Selective Catalytic Reduction of NO x
journal, June 2018

Temperature-dependent dynamics of NH ₃ -derived Cu species in the Cu-CHA SCR catalyst
journal, January 2019

Promotional effect of the TiO ₂ (001) facet in the selective catalytic reduction of NO with NH ₃ : in situ DRIFTS and DFT studies
journal, January 2016

Catalytic oxidation of NO over MnO ₂ with different crystal structures
journal, January 2016

The correlation between surface defects and the behavior of hydrogen adsorption over ZnO under UV light irradiation
journal, January 2018

Quantitative determination of the Cu species, acid sites and NH ₃ -SCR mechanism on Cu-SSZ-13 and H-SSZ-13 at low temperatures
journal, January 2020

The dynamic nature of Cu sites in Cu-SSZ-13 and the origin of the seagull NOx conversion profile during NH3-SCR
null, January 2019