skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Mechanism by which Tungsten Oxide Promotes the Activity of Supported V2O5/TiO2 Catalysts for NOX Abatement: Structural Effects Revealed by 51V MAS NMR Spectroscopy

Abstract

Growing concern for environmental pollutants coupled with an expansion of energy demand has promoted significant interest in technologies to abate contaminating species. Nitrogen oxides are particularly alarming due to their numerous detrimental impacts to the environment and public health, where selective catalytic reduction to inert N2 is an industrially-relevant mitigation technology. Herein, we provide unique, molecular-level insight on the structure and reactivity of V2O5(-WO3)/TiO2 catalysts employed at stationary facilities for NOx removal. Detailed catalytic testing, spectroscopy (nuclear magnetic resonance, Raman, and electron paramagnetic resonance), and electronic structure-based predictions of 51V chemical shifts help clarify the promotional role of tungsten oxide and identify an active site requirement for SCR of NOx. We show that progressive addition of vanadia to the catalyst surface increases the catalytic SCR performance and promotes the formation of larger vanadium domains, demonstrating the proportional relationship of SCR reaction rate to [VOx loading]2 for supported V2O5/TiO2 catalysts with increasing surface vanadia coverage. Tungsten oxide incorporation enhances catalyst reactivity which is shown to stem not from electronic effects, but from changes to the vanadium structure as observed spectroscopically. The progressive addition of tungsten oxide to the catalyst surface also increases the catalytic performance and promotes the formation of largermore » vanadium domains, which are beneficial for catalytic turnover in a two-site model. Further, unique monomeric species are confidently ascribed to distorted tetrahedral and square pyramidal structures, resolving a long-standing uncertainty in literature assignments for the signals. These findings provide strong support for both the dual-site requirement for the SCR reaction and the important structural promotional effect that tungsten offers for mitigation of these harmful pollutants.« less

Authors:
ORCiD logo [1];  [2];  [3];  [3];  [4];  [4];  [3];  [3];  [3];  [3];  [2];  [1]; ORCiD logo [3]
+ Show Author Affiliations
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)
  2. Lehigh Univ., Bethlehem, PA (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. The Univ. of Alabama, Tuscaloosa, AL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1572978
Alternate Identifier(s):
OSTI ID: 1547078
Report Number(s):
PNNL-SA-141251
Journal ID: ISSN 1433-7851; ANIE; TRN: US2001090
Grant/Contract Number:  
AC05-76RL01830; SC0012577; 66628
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 36; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heterogeneous catalysis; NMR spectroscopy; NOx; selective catalytic reduction (SCR); vanadium

Citation Formats

Jaegers, Nicholas R., Lai, Jun-Kun, He, Yang, Walter, Eric, Dixon, David A., Vasiliu, Monica, Chen, Ying, Wang, Chongmin, Hu, Mary Y., Mueller, Karl T., Wachs, Israel E., Wang, Yong, and Hu, Jian Zhi. Mechanism by which Tungsten Oxide Promotes the Activity of Supported V2O5/TiO2 Catalysts for NOX Abatement: Structural Effects Revealed by 51V MAS NMR Spectroscopy. United States: N. p., 2019. Web. doi:10.1002/anie.201904503.
Copy to clipboard
Jaegers, Nicholas R., Lai, Jun-Kun, He, Yang, Walter, Eric, Dixon, David A., Vasiliu, Monica, Chen, Ying, Wang, Chongmin, Hu, Mary Y., Mueller, Karl T., Wachs, Israel E., Wang, Yong, & Hu, Jian Zhi. Mechanism by which Tungsten Oxide Promotes the Activity of Supported V2O5/TiO2 Catalysts for NOX Abatement: Structural Effects Revealed by 51V MAS NMR Spectroscopy. United States. doi:10.1002/anie.201904503.
Copy to clipboard
Jaegers, Nicholas R., Lai, Jun-Kun, He, Yang, Walter, Eric, Dixon, David A., Vasiliu, Monica, Chen, Ying, Wang, Chongmin, Hu, Mary Y., Mueller, Karl T., Wachs, Israel E., Wang, Yong, and Hu, Jian Zhi. Mon . "Mechanism by which Tungsten Oxide Promotes the Activity of Supported V2O5/TiO2 Catalysts for NOX Abatement: Structural Effects Revealed by 51V MAS NMR Spectroscopy". United States. doi:10.1002/anie.201904503. https://www.osti.gov/servlets/purl/1572978.
Copy to clipboard
@article{osti_1572978,
title = {Mechanism by which Tungsten Oxide Promotes the Activity of Supported V2O5/TiO2 Catalysts for NOX Abatement: Structural Effects Revealed by 51V MAS NMR Spectroscopy},
author = {Jaegers, Nicholas R. and Lai, Jun-Kun and He, Yang and Walter, Eric and Dixon, David A. and Vasiliu, Monica and Chen, Ying and Wang, Chongmin and Hu, Mary Y. and Mueller, Karl T. and Wachs, Israel E. and Wang, Yong and Hu, Jian Zhi},
abstractNote = {Growing concern for environmental pollutants coupled with an expansion of energy demand has promoted significant interest in technologies to abate contaminating species. Nitrogen oxides are particularly alarming due to their numerous detrimental impacts to the environment and public health, where selective catalytic reduction to inert N2 is an industrially-relevant mitigation technology. Herein, we provide unique, molecular-level insight on the structure and reactivity of V2O5(-WO3)/TiO2 catalysts employed at stationary facilities for NOx removal. Detailed catalytic testing, spectroscopy (nuclear magnetic resonance, Raman, and electron paramagnetic resonance), and electronic structure-based predictions of 51V chemical shifts help clarify the promotional role of tungsten oxide and identify an active site requirement for SCR of NOx. We show that progressive addition of vanadia to the catalyst surface increases the catalytic SCR performance and promotes the formation of larger vanadium domains, demonstrating the proportional relationship of SCR reaction rate to [VOx loading]2 for supported V2O5/TiO2 catalysts with increasing surface vanadia coverage. Tungsten oxide incorporation enhances catalyst reactivity which is shown to stem not from electronic effects, but from changes to the vanadium structure as observed spectroscopically. The progressive addition of tungsten oxide to the catalyst surface also increases the catalytic performance and promotes the formation of larger vanadium domains, which are beneficial for catalytic turnover in a two-site model. Further, unique monomeric species are confidently ascribed to distorted tetrahedral and square pyramidal structures, resolving a long-standing uncertainty in literature assignments for the signals. These findings provide strong support for both the dual-site requirement for the SCR reaction and the important structural promotional effect that tungsten offers for mitigation of these harmful pollutants.},
doi = {10.1002/anie.201904503},
journal = {Angewandte Chemie (International Edition)},
number = 36,
volume = 58,
place = {United States},
year = {2019},
month = {7}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI:  10.1002/anie.201904503
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Mechanism of the reaction of nitric oxide, ammonia, and oxygen over vanadia catalysts. 2. Isotopic transient studies with oxygen-18 and nitrogen-15
journal, December 1987

  • Janssen, Frans J. J. G.; Van den Kerkhof, Frans M. G.; Bosch, Hans.
  • The Journal of Physical Chemistry, Vol. 91, Issue 27
  • DOI: 10.1021/j100311a016

Characterization by solid state 51V NMR spectroscopy
journal, March 2000

Nature of Active Sites and Surface Intermediates during SCR of NO with NH 3 by Supported V 2 O 5 –WO 3 /TiO 2 Catalysts
journal, October 2017

  • Zhu, Minghui; Lai, Jun-Kun; Tumuluri, Uma
  • Journal of the American Chemical Society, Vol. 139, Issue 44
  • DOI: 10.1021/jacs.7b09646

Surface structures of supported tungsten oxide catalysts under dehydrated conditions
journal, March 1996

  • Kim, Du Soung; Ostromecki, Marlene; Wachs, Israel E.
  • Journal of Molecular Catalysis A: Chemical, Vol. 106, Issue 1-2
  • DOI: 10.1016/1381-1169(95)00186-7

Investigation of the Mechanism of Ammonia Oxidation and Oxygen Exchange over Vanadia Catalysts Using N-15 and O-18 Tracer Studies
journal, October 1994

  • Ozkan, U. S.; Cai, Y. P.; Kumthekar, M. W.
  • Journal of Catalysis, Vol. 149, Issue 2
  • DOI: 10.1006/jcat.1994.1305

Oxidation of SO2over Supported Metal Oxide Catalysts
journal, January 1999

  • Dunn, Joseph P.; Stenger, Harvey G.; Wachs, Israel E.
  • Journal of Catalysis, Vol. 181, Issue 2
  • DOI: 10.1006/jcat.1998.2305

Characteristics of V2O5 supported on sulfated TiO2 for selective catalytic reduction of NO by NH3
journal, August 2000

Chemical and mechanistic aspects of the selective catalytic reduction of NO by ammonia over oxide catalysts: A review
journal, September 1998

Structural determination of supported vanadium pentoxide-tungsten trioxide-titania catalysts by in situ Raman spectroscopy and x-ray photoelectron spectroscopy
journal, November 1991

  • Vuurman, Michael A.; Wachs, Israel E.; Hirt, Andrew M.
  • The Journal of Physical Chemistry, Vol. 95, Issue 24
  • DOI: 10.1021/j100177a059

Surface characterization studies of TiO2 supported manganese oxide catalysts for low temperature SCR of NO with NH3
journal, October 2007

  • Ettireddy, Padmanabha Reddy; Ettireddy, Neeraja; Mamedov, Sergey
  • Applied Catalysis B: Environmental, Vol. 76, Issue 1-2
  • DOI: 10.1016/j.apcatb.2007.05.010

Reactivity and Physicochemical Characterization of V2O5-WO3/TiO2 De-NO Catalysts
journal, August 1995

  • Alemany, L. J.; Lietti, L.; Ferlazzo, N.
  • Journal of Catalysis, Vol. 155, Issue 1
  • DOI: 10.1006/jcat.1995.1193

Influences of impregnation procedure on the SCR activity and alkali resistance of V2O5–WO3/TiO2 catalyst
journal, October 2013

Polymeric vanadyl species determine the low-temperature activity of V-based catalysts for the SCR of NO x with NH 3
journal, November 2018

VOx Surface Coverage Optimization of V2O5/WO3-TiO2 SCR Catalysts by Variation of the V Loading and by Aging
journal, October 2015

  • Marberger, Adrian; Elsener, Martin; Ferri, Davide
  • Catalysts, Vol. 5, Issue 4
  • DOI: 10.3390/catal5041704

Reactivity of Supported Vanadium Oxide Catalysts: The Partial Oxidation of Methanol
journal, April 1994

Spectroscopic investigation of vanadium speciation in vanadium-doped nanocrystalline anatase
journal, January 1997

  • Luca, Victor; Thomson, Stuart; Howe, Russell F.
  • Journal of the Chemical Society, Faraday Transactions, Vol. 93, Issue 12
  • DOI: 10.1039/a608569e

Selective Catalytic Reduction of NO with NH3over Supported Vanadia Catalysts
journal, June 1996

  • Wachs, Israel E.; Deo, Goutam; Weckhuysen, Bert M.
  • Journal of Catalysis, Vol. 161, Issue 1
  • DOI: 10.1006/jcat.1996.0179

Mechanistic studies of selective catalytic reduction of nitric oxide with ammonia over V2O5/TiO2 (anatase) catalysts through transient isotopic labeling at steady state
journal, February 1995

  • Ozkan, Umit S.; Cai, Yeping; Kumthekar, Mahesh W.
  • The Journal of Physical Chemistry, Vol. 99, Issue 8
  • DOI: 10.1021/j100008a019

Periodic density functional theory studies of the VOx/TiO2 (anatase) catalysts: Structure and stability of monomeric species
journal, June 2012

Surface characterization studies on the interaction of V2O5–WO3/TiO2 catalyst for low temperature SCR of NO with NH3
journal, January 2015

Nanocrystalline Anatase Titania-Supported Vanadia Catalysts: Facet-Dependent Structure of Vanadia
journal, June 2015

  • Li, Wei-Zhen; Gao, Feng; Li, Yan
  • The Journal of Physical Chemistry C, Vol. 119, Issue 27
  • DOI: 10.1021/acs.jpcc.5b01486

Achieving Atomic Dispersion of Highly Loaded Transition Metals in Small-Pore Zeolite SSZ-13: High-Capacity and High-Efficiency Low-Temperature CO and Passive NO x Adsorbers
journal, November 2018

  • Khivantsev, Konstantin; Jaegers, Nicholas R.; Kovarik, Libor
  • Angewandte Chemie International Edition, Vol. 57, Issue 51
  • DOI: 10.1002/anie.201809343

Coexistence of Square Pyramidal Structures of Oxo Vanadium (+5) and (+4) Species Over Low-Coverage VO X /TiO 2 (101) and (001) Anatase Catalysts
journal, October 2015

  • Arnarson, Logi; Rasmussen, Søren B.; Falsig, Hanne
  • The Journal of Physical Chemistry C, Vol. 119, Issue 41
  • DOI: 10.1021/acs.jpcc.5b06132

Investigation of Silica-Supported Vanadium Oxide Catalysts by High-Field 51 V Magic-Angle Spinning NMR
journal, March 2017

  • Jaegers, Nicholas R.; Wan, Chuan; Hu, Mary Y.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 11
  • DOI: 10.1021/acs.jpcc.7b01658

Effect of water vapor on the molecular structures of supported vanadium oxide catalysts at elevated temperatures
journal, July 1996

  • Jehng, Jih-Mirn; Deo, Goutam; Weckhuysen, Bert M.
  • Journal of Molecular Catalysis A: Chemical, Vol. 110, Issue 1
  • DOI: 10.1016/1381-1169(96)00061-1

Trends in NOx abatement: A review
journal, September 2010

Quantitative Determination of the Speciation of Surface Vanadium Oxides and Their Catalytic Activity
journal, May 2006

  • Tian, Hanjing; Ross, Elizabeth I.; Wachs, Israel E.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 19
  • DOI: 10.1021/jp055767y

Solid-state vanadium-51 NMR structural studies on supported vanadium(V) oxide catalysts: vanadium oxide surface layers on alumina and titania supports
journal, September 1989

  • Eckert, Hellmut; Wachs, Israel E.
  • The Journal of Physical Chemistry, Vol. 93, Issue 18
  • DOI: 10.1021/j100355a043

Molecular structure–reactivity relationships for the oxidation of sulfur dioxide over supported metal oxide catalysts
journal, November 1999

Role of WO3 in mixed V2O5-WO3/TiO2catalysts for selective catalytic reduction of nitric oxide with ammonia
journal, January 1992

Catalysis science of supported vanadium oxide catalysts
journal, January 2013

The Significance of Lewis Acid Sites for the Selective Catalytic Reduction of Nitric Oxide on Vanadium-Based Catalysts
journal, August 2016

  • Marberger, Adrian; Ferri, Davide; Elsener, Martin
  • Angewandte Chemie International Edition, Vol. 55, Issue 39
  • DOI: 10.1002/anie.201605397

Role of WO 3 in the Hg Oxidation across the V 2 O 5 –WO 3 –TiO 2 SCR Catalyst: A DFT Study
journal, November 2013

  • Suarez Negreira, Ana; Wilcox, Jennifer
  • The Journal of Physical Chemistry C, Vol. 117, Issue 46
  • DOI: 10.1021/jp407794g

A new view on the relations between tungsten and vanadium in V2O5WO3/TiO2 catalysts for the selective reduction of NO with NH3
journal, February 2012

Characterization of tungsta-titania catalysts
journal, July 1992

The Complete 51 V MAS NMR Spectrum of Surface Vanadia Nanoparticles on Anatase (TiO 2 ):  Vanadia Surface Structure of a DeNO x Catalyst
journal, April 2004

  • Nielsen, Ulla Gro; Topsøe, Nan-Yu; Brorson, Michael
  • Journal of the American Chemical Society, Vol. 126, Issue 15
  • DOI: 10.1021/ja030091a

Solid-State Vanadium-51 NMR Studies of Supported V 2 O 5 −WO 3 /TiO 2 Catalysts
journal, March 2000

  • Gheorghe, Claudia; Gee, Becky
  • Chemistry of Materials, Vol. 12, Issue 3
  • DOI: 10.1021/cm990416f

Dispersion of tungsten oxide on SCR performance of V2O5WO3/TiO2: Acidity, surface species and catalytic activity
journal, June 2013

Oxidative dehydrogenation of isobutane over vanadia catalysts supported by titania nanoshapes
journal, April 2016

Role of WO3 in NO Reduction with NH3 over V2O5-WO3/TiO2: A New Insight from the Kinetic Study
journal, September 2016

Visualizing atomic-scale redox dynamics in vanadium oxide-based catalysts
journal, August 2017

Reaction Pathways and Kinetics for Selective Catalytic Reduction (SCR) of Acidic NO x Emissions from Power Plants with NH 3
journal, November 2017

Selective catalytic reduction of NO by NH3 with WO3-TiO2 catalysts: Influence of catalyst synthesis method
journal, July 2016

Steady-State and Transient Reactivity Study of TiO 2 -Supported V 2 O 5 −WO 3 De-NO x Catalysts:  Relevance of the Vanadium−Tungsten Interaction on the Catalytic Activity
journal, January 1996

  • Lietti, Luca; Forzatti, Pio; Bregani, Fiorenzo
  • Industrial & Engineering Chemistry Research, Vol. 35, Issue 11
  • DOI: 10.1021/ie960158l

The Significance of Lewis Acid Sites for the Selective Catalytic Reduction of Nitric Oxide on Vanadium-Based Catalysts
journal, August 2016

  • Marberger, Adrian; Ferri, Davide; Elsener, Martin
  • Angewandte Chemie, Vol. 128, Issue 39
  • DOI: 10.1002/ange.201605397

Vanadia-Titania Catalysts for Selective Catalytic Reduction of Nitric-Oxide by Ammonia
journal, January 1995

  • Topsoe, N. Y.; Dumesic, J. A.; Topsoe, H.
  • Journal of Catalysis, Vol. 151, Issue 1
  • DOI: 10.1006/jcat.1995.1025

Review on the latest developments in modified vanadium-titanium-based SCR catalysts
journal, August 2018

Chemical poison and regeneration of SCR catalysts for NO x removal from stationary sources
journal, March 2016

  • Li, Junhua; Peng, Yue; Chang, Huazhen
  • Frontiers of Environmental Science & Engineering, Vol. 10, Issue 3
  • DOI: 10.1007/s11783-016-0832-3

The reaction mechanism for the SCR process on monomer V 5+ sites and the effect of modified Brønsted acidity
journal, January 2016

  • Arnarson, Logi; Falsig, Hanne; Rasmussen, Søren B.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 25
  • DOI: 10.1039/C6CP02274J

Influence of catalyst synthesis method on selective catalytic reduction (SCR) of NO by NH3 with V2O5-WO3/TiO2 catalysts
journal, September 2016

    [ × clear filter / sort ]

    Works referencing / citing this record:

    Structural characterization of vanadium environments in MCM-41 molecular sieve catalysts by solid state 51 V NMR
    journal, January 2019

    • de Oliveira, Marcos; Seeburg, Dominik; Weiß, Jana
    • Catalysis Science & Technology, Vol. 9, Issue 21
    • DOI: 10.1039/c9cy01410a

    Effect of treatment atmosphere on the vanadium species of V/TiO 2 catalysts for the selective catalytic reduction of NO x with NH 3
    journal, January 2020

    • Lian, Zhihua; Xin, Shaohui; Zhu, Na
    • Catalysis Science & Technology, Vol. 10, Issue 2
    • DOI: 10.1039/c9cy01888c
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: