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Title: Influence of catalyst synthesis method on selective catalytic reduction (SCR) of NO by NH3 with V2O5-WO3/TiO2 catalysts

Abstract

We compared the molecular structures, surface acidity and catalytic activity for NO/NH3/O2 SCR of V2O5-WO3/TiO2 catalysts for two different synthesis methods: co-precipitation of aqueous vanadium and tungsten oxide precursors with TiO(OH)2 and by incipient wetness impregnation of the aqueous precursors on a reference crystalline TiO2 support (P25; primarily anatase phase). Bulk analysis by XRD showed that co-precipitation results in small and/or poorly ordered TiO2(anatase) particles and that VOx and WOx do not form solid solutions with the bulk titania lattice. Surface analysis of the co-precipitated catalyst by High Sensitivity-Low Energy Ion Scattering (HS-LEIS) confirms that the VOx and WOx are surface segregated for the co-precipitated catalysts. In situ Raman and IR spectroscopy revealed that the vanadium and tungsten oxide components are present as surface mono-oxo O = VO3 and O = WO4 sites on the TiO2 supports. Co-precipitation was shown for the first time to also form new mono-oxo surface VO4 and WO4 sites that appear to be anchored at surface defects of the TiO2 support. IR analysis of chemisorbed ammonia showed the presence of both surface NH3* on Lewis acid sites and surface NH4+* on Brønsted acid sites. TPSR spectroscopy demonstrated that the specific SCR kinetics was controlled bymore » the redox surface VO4 species and that the surface kinetics was independent of TiO2 synthesis method or presence of surface WO5 sites. SCR reaction studies revealed that the surface WO5 sites possess minimal activity below ~325 °C and their primary function is to increase the adsorption capacity of ammonia. A relationship between the SCR activity and surface acidity was not found. The SCR reaction is controlled by the surface VO4 sites that initiate the reaction at ~200 °C. The co-precipitated catalysts were always more active than the corresponding impregnated catalysts. Finally, we ascribe the higher activity of the co-precipitated catalysts to the presence of the new surface WOx sites associated surface defects on the TiO2 support that increase the ammonia adsorption capacity.« less

Authors:
 [1];  [2];  [2];  [3];  [4];  [4];  [2]
  1. Chongqing Univ., Chongqing (China). College of Materials Science and Engineering; Lehigh Univ., Bethlehem, PA (United States). Operando Molecular Spectroscopy & Catalysis Lab.
  2. Lehigh Univ., Bethlehem, PA (United States). Operando Molecular Spectroscopy & Catalysis Lab.
  3. Chongqing Univ., Chongqing (China). College of Materials Science and Engineering
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Science Division and Center for Nanophase Materials Sciences
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1295102
Alternate Identifier(s):
OSTI ID: 1341096
Grant/Contract Number:  
AC05-00OR22725; SC0012577; 51274263; 51204220; UNCAGE-ME
Resource Type:
Accepted Manuscript
Journal Name:
Applied Catalysis B: Environmental
Additional Journal Information:
Journal Volume: 193; Journal Issue: C; Journal ID: ISSN 0926-3373
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Catalysts; Supported; TiO2; V2O5; WO3; Synthesis; Co-precipitation; Incipient-wetness impregnation; Selective catalytic reduction (SCR); NO; NH3; O2; Spectroscopy; Raman; Infrared; TPSR; HS-LEIS; XRD

Citation Formats

He, Yuanyuan, Ford, Michael E., Zhu, Minghui, Liu, Qingcai, Tumuluri, Uma, Wu, Zili, and Wachs, Israel E.. Influence of catalyst synthesis method on selective catalytic reduction (SCR) of NO by NH3 with V2O5-WO3/TiO2 catalysts. United States: N. p., 2016. Web. https://doi.org/10.1016/j.apcatb.2016.04.022.
He, Yuanyuan, Ford, Michael E., Zhu, Minghui, Liu, Qingcai, Tumuluri, Uma, Wu, Zili, & Wachs, Israel E.. Influence of catalyst synthesis method on selective catalytic reduction (SCR) of NO by NH3 with V2O5-WO3/TiO2 catalysts. United States. https://doi.org/10.1016/j.apcatb.2016.04.022
He, Yuanyuan, Ford, Michael E., Zhu, Minghui, Liu, Qingcai, Tumuluri, Uma, Wu, Zili, and Wachs, Israel E.. Thu . "Influence of catalyst synthesis method on selective catalytic reduction (SCR) of NO by NH3 with V2O5-WO3/TiO2 catalysts". United States. https://doi.org/10.1016/j.apcatb.2016.04.022. https://www.osti.gov/servlets/purl/1295102.
@article{osti_1295102,
title = {Influence of catalyst synthesis method on selective catalytic reduction (SCR) of NO by NH3 with V2O5-WO3/TiO2 catalysts},
author = {He, Yuanyuan and Ford, Michael E. and Zhu, Minghui and Liu, Qingcai and Tumuluri, Uma and Wu, Zili and Wachs, Israel E.},
abstractNote = {We compared the molecular structures, surface acidity and catalytic activity for NO/NH3/O2 SCR of V2O5-WO3/TiO2 catalysts for two different synthesis methods: co-precipitation of aqueous vanadium and tungsten oxide precursors with TiO(OH)2 and by incipient wetness impregnation of the aqueous precursors on a reference crystalline TiO2 support (P25; primarily anatase phase). Bulk analysis by XRD showed that co-precipitation results in small and/or poorly ordered TiO2(anatase) particles and that VOx and WOx do not form solid solutions with the bulk titania lattice. Surface analysis of the co-precipitated catalyst by High Sensitivity-Low Energy Ion Scattering (HS-LEIS) confirms that the VOx and WOx are surface segregated for the co-precipitated catalysts. In situ Raman and IR spectroscopy revealed that the vanadium and tungsten oxide components are present as surface mono-oxo O = VO3 and O = WO4 sites on the TiO2 supports. Co-precipitation was shown for the first time to also form new mono-oxo surface VO4 and WO4 sites that appear to be anchored at surface defects of the TiO2 support. IR analysis of chemisorbed ammonia showed the presence of both surface NH3* on Lewis acid sites and surface NH4+* on Brønsted acid sites. TPSR spectroscopy demonstrated that the specific SCR kinetics was controlled by the redox surface VO4 species and that the surface kinetics was independent of TiO2 synthesis method or presence of surface WO5 sites. SCR reaction studies revealed that the surface WO5 sites possess minimal activity below ~325 °C and their primary function is to increase the adsorption capacity of ammonia. A relationship between the SCR activity and surface acidity was not found. The SCR reaction is controlled by the surface VO4 sites that initiate the reaction at ~200 °C. The co-precipitated catalysts were always more active than the corresponding impregnated catalysts. Finally, we ascribe the higher activity of the co-precipitated catalysts to the presence of the new surface WOx sites associated surface defects on the TiO2 support that increase the ammonia adsorption capacity.},
doi = {10.1016/j.apcatb.2016.04.022},
journal = {Applied Catalysis B: Environmental},
number = C,
volume = 193,
place = {United States},
year = {2016},
month = {4}
}

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Cited by: 16 works
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Works referenced in this record:

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


Recent Advances in De‐NOxing Catalysis for Stationary Applications
journal, March 1996


Effect of operating variables on the enhanced SCR reaction over a commercial V2O5–WO3/TiO2 catalyst for stationary applications
journal, April 2012


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

Systematic mechanism study of the high temperature SCR of NO by NH3 over a W/TiO2 catalyst
journal, September 2012


The effect of metal oxide additives on the activity of V2O5/TiO2 catalysts for the selective catalytic reduction of nitric oxide by ammonia
journal, February 1999

  • Amiridis, Michael D.; Duevel, Robert V.; Wachs, Israel E.
  • Applied Catalysis B: Environmental, Vol. 20, Issue 2
  • DOI: 10.1016/S0926-3373(98)00101-5

Reactivity of V2O5Catalysts for the Selective Catalytic Reduction of NO by NH3: Influence of Vanadia Loading, H2O, and SO2
journal, June 1996

  • Amiridis, Michael D.; Wachs, Israel E.; Deo, Goutam
  • Journal of Catalysis, Vol. 161, Issue 1
  • DOI: 10.1006/jcat.1996.0182

Preparation and properties of vanadia/titania monolayer catalysts
journal, September 1997


Effect of vanadia and tungsten loadings on the physical and chemical characteristics of V2O5-WO3/TiO2 catalysts
journal, February 2004


Study of anatase–rutile transition phase in monolithic catalyst V2O5/TiO2 and V2O5–WO3/TiO2
journal, February 2001


Thermal stability of vanadia-tungsta-titania catalysts in the SCR process
journal, November 2002


Study of thermal deactivation of a de-NOx commercial catalyst
journal, December 2001


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

  • Topsoe, N. Y.; Topsoe, H.; Dumesic, J. A.
  • Journal of Catalysis, Vol. 151, Issue 1
  • DOI: 10.1006/jcat.1995.1024

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

Selective Catalytic Reduction of NO with NH3 on SO−24/TiO2 Superacid Catalyst
journal, January 1993


Fundamental Studies of Butane Oxidation over Model-Supported Vanadium Oxide Catalysts: Molecular Structure-Reactivity Relationships
journal, August 1997

  • Wachs, Israel E.; Jehng, Jih-Mirn; Deo, Goutam
  • Journal of Catalysis, Vol. 170, Issue 1
  • DOI: 10.1006/jcat.1997.1742

Acidic properties and stability of sulfate-promoted metal oxides
journal, February 1992


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

Monitoring surface metal oxide catalytic active sites with Raman spectroscopy
journal, January 2010

  • Wachs, Israel E.; Roberts, Charles A.
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/c0cs00145g

Structure and Catalytic Properties of Supported Vanadium Oxides: Support Effects on Oxidative Dehydrogenation Reactions
journal, January 1999

  • Khodakov, Andrei; Olthof, Bryan; Bell, Alexis T.
  • Journal of Catalysis, Vol. 181, Issue 2
  • DOI: 10.1006/jcat.1998.2295

Laser Raman spectroscopy of supported vanadium oxide catalysts
journal, May 1990

  • Went, Gregory T.; Oyama, S. Ted.; Bell, Alexis T.
  • The Journal of Physical Chemistry, Vol. 94, Issue 10
  • DOI: 10.1021/j100373a067

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


Effect of grafting sequence on the behavior of titania-supported v VO-WO catalysts in the selective reduction of NO by NH
journal, June 2000


Vanadia and tungsta grafted on TiO2: influence of the grafting sequence on structural and chemical properties
journal, May 2000


Flame-made WO3/TiO2 nanoparticles: Relation between surface acidity, structure and photocatalytic activity
journal, February 2008

  • Akurati, Kranthi K.; Vital, Andri; Dellemann, Jean-Philippe
  • Applied Catalysis B: Environmental, Vol. 79, Issue 1
  • DOI: 10.1016/j.apcatb.2007.09.036

Quantitative relationship between the nature of surface species and the catalytic activity of tungsten oxides supported on crystallized titania
journal, March 2010

  • Onfroy, Thomas; Lebarbier, Vanessa; Clet, Guillaume
  • Journal of Molecular Catalysis A: Chemical, Vol. 318, Issue 1-2
  • DOI: 10.1016/j.molcata.2009.11.013

Influence of calcination treatment on the structure of grafted WOx species on titania
journal, February 1999


Relations between Structure, Acidity, and Activity of WO x /TiO 2 :  Influence of the Initial State of the Support, Titanium Oxyhydroxide, or Titanium Oxide
journal, November 2006

  • Lebarbier, Vanessa; Clet, Guillaume; Houalla, Marwan
  • The Journal of Physical Chemistry B, Vol. 110, Issue 45
  • DOI: 10.1021/jp064202e

Conversion of 1-butene over WO3-TiO2 Catalysts
journal, January 1994


Preparation of selective catalytic reduction catalysts via milling and thermal spreading
journal, November 1997


Anomalous reactivity of supported V2O5 nanoparticles for propane oxidative dehydrogenation: influence of the vanadium oxide precursor
journal, January 2013

  • Carrero, Carlos A.; Keturakis, Christopher J.; Orrego, Andres
  • Dalton Transactions, Vol. 42, Issue 35
  • DOI: 10.1039/c3dt50611h

Recommendations for the characterization of porous solids (Technical Report)
journal, January 1994

  • Rouquerol, J.; Avnir, D.; Fairbridge, C. W.
  • Pure and Applied Chemistry, Vol. 66, Issue 8, p. 1739-1758
  • DOI: 10.1351/pac199466081739

Physical and chemical characterization of surface vanadium oxide supported on titania: influence of the titania phase (anatase, rutile, brookite and B)
journal, November 1992


Tuning the Electronic and Molecular Structures of Catalytic Active Sites with Titania Nanoligands
journal, January 2009

  • Ross-Medgaarden, Elizabeth I.; Wachs, Israel E.; Knowles, William V.
  • Journal of the American Chemical Society, Vol. 131, Issue 2
  • DOI: 10.1021/ja711456c

Oxide phonon spectra
journal, January 1969

  • Beattie, I. R.; Gilson, T. R.
  • Journal of the Chemical Society A: Inorganic, Physical, Theoretical
  • DOI: 10.1039/j19690002322

Structural Determination of Bulk and Surface Tungsten Oxides with UV−vis Diffuse Reflectance Spectroscopy and Raman Spectroscopy
journal, September 2007

  • Ross-Medgaarden, Elizabeth I.; Wachs, Israel E.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 41
  • DOI: 10.1021/jp074219c

Catalysis science of the solid acidity of model supported tungsten oxide catalysts
journal, August 2006


Effects of CeO2 support facets on VOx/CeO2 catalysts in oxidative dehydrogenation of methanol
journal, June 2014


Reactivity of V2O5-WO3/TiO2 catalysts in the selective catalytic reduction of nitric oxide by ammonia
journal, May 1996


An FT-IR study of ammonia adsorption and oxidation over anatase-supported metal oxides
journal, September 1997

  • Amores, JosèManuel Gallardo; Escribano, Vicente Sanchez; Ramis, Gianguido
  • Applied Catalysis B: Environmental, Vol. 13, Issue 1
  • DOI: 10.1016/S0926-3373(96)00092-6

Dynamics of the SCR-DeNOx reaction by the transient-response method
journal, October 1997

  • Lietti, Luca; Nova, Isabella; Camurri, Stefano
  • AIChE Journal, Vol. 43, Issue 10
  • DOI: 10.1002/aic.690431017

Characterization of tungsta-titania catalysts
journal, July 1992


STAFF-INDUSTRY COLLABORATIVE REPORT Vapor-Phase Production of Colloidal Silica
journal, March 1959

  • White, Laurence; Duffy, George
  • Industrial & Engineering Chemistry, Vol. 51, Issue 3
  • DOI: 10.1021/ie51394a019

Resolving the Atomic Structure of Vanadia Monolayer Catalysts: Monomers, Trimers, and Oligomers on Ceria
journal, October 2009

  • Baron, Martin; Abbott, Heather; Bondarchuk, Oleksandr
  • Angewandte Chemie International Edition, Vol. 48, Issue 43
  • DOI: 10.1002/anie.200903085

Molecular/electronic structure–surface acidity relationships of model-supported tungsten oxide catalysts
journal, March 2007


Reaction-Induced Spreading of Metal Oxides onto Surfaces of Oxide Supports during Alcohol Oxidation:  Phenomenon, Nature, and Mechanisms
journal, February 1999

  • Wang, Chuan-Bao; Cai, Yeping; Wachs, Israel E.
  • Langmuir, Vol. 15, Issue 4
  • DOI: 10.1021/la9807210

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

An EPR Study of the Surface Chemistry of the V2O5–WO3/TiO2Catalyst: Redox Behaviour and State of V(IV)
journal, March 1997

  • Paganini, Maria Cristina; Dall'Acqua, Lorenzo; Giamello, Elio
  • Journal of Catalysis, Vol. 166, Issue 2
  • DOI: 10.1006/jcat.1997.1492

Recent conceptual advances in the catalysis science of mixed metal oxide catalytic materials
journal, February 2005


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

The effects of structure on the catalytic activity and selectivity of V2O5/TiO2 for the reduction of NO by NH3
journal, April 1992


    Works referencing / citing this record:

    TiO 2 –SiO 2 supported MnWO x catalysts by liquid-phase deposition for low-temperature NH 3 -SCR
    journal, January 2019

    • Lu, Weizhe; Lu, Hanfeng; Zhang, Zekai
    • Royal Society Open Science, Vol. 6, Issue 1
    • DOI: 10.1098/rsos.180669

    DFT and experimental study on denitration mechanism over VPO/TiO2 catalyst
    journal, February 2019


    Comprehensive study of the promotional mechanism of F on Ce–Mo/TiO 2 catalysts for wide temperature NH 3 -SCR performance: the activation of surface Ti–F bonds
    journal, January 2019

    • Zhang, Guodong; Huang, Xiaosheng; Yang, Xing
    • Catalysis Science & Technology, Vol. 9, Issue 9
    • DOI: 10.1039/c9cy00256a

    A zeolitic vanadotungstate family with structural diversity and ultrahigh porosity for catalysis
    journal, September 2018


    Low-temperature co-purification of NOx and Hg0 from simulated flue gas by CexZryMnzO2/r-Al2O3: the performance and its mechanism
    journal, May 2018

    • Lu, Pei; Yue, Huifang; Xing, Yi
    • Environmental Science and Pollution Research, Vol. 25, Issue 21
    • DOI: 10.1007/s11356-018-2199-4

    Alkali-driven active site shift of fast SCR with NH 3 on V 2 O 5 –WO 3 /TiO 2 catalyst via a novel Eley–Rideal mechanism
    journal, January 2019

    • Xiang, Jinyao; Du, Xuesen; Wan, Yuyi
    • Catalysis Science & Technology, Vol. 9, Issue 21
    • DOI: 10.1039/c9cy01565e

    Thermal stability of Si-doped V2O5/WO3–TiO2 for selective catalytic reduction of NOx by NH3
    journal, December 2018


    One-pot synthesis of framework W-doped TS-1 zeolite with robust Lewis acidity for effective oxidative desulfurization
    journal, January 2019

    • Lv, Guojun; Deng, Senlin; Yi, Zhai
    • Chemical Communications, Vol. 55, Issue 33
    • DOI: 10.1039/c9cc00715f

    Simultaneous removal of SO 2 and NO x from flue gas by wet scrubbing using a urea solution
    journal, March 2018


    Research Status and Prospect on Vanadium-Based Catalysts for NH3-SCR Denitration
    journal, September 2018

    • Zhang, Jie; Li, Xiangcheng; Chen, Pingan
    • Materials, Vol. 11, Issue 9
    • DOI: 10.3390/ma11091632

    Mechanism by which Tungsten Oxide Promotes the Activity of Supported V 2 O 5 /TiO 2 Catalysts for NO X Abatement: Structural Effects Revealed by 51 V MAS NMR Spectroscopy
    journal, September 2019

    • Jaegers, Nicholas R.; Lai, Jun‐Kun; He, Yang
    • Angewandte Chemie International Edition, Vol. 58, Issue 36
    • DOI: 10.1002/anie.201904503

    Effect of Ag–Fe–Cu tri-metal loading in bismuth oxybromide to develop a novel nanocomposite for the sunlight driven photocatalytic oxidation of alcohols
    journal, January 2019

    • Bisht, Narendra Singh; Pancholi, Deepika; Sahoo, Nanda Gopal
    • Catalysis Science & Technology, Vol. 9, Issue 15
    • DOI: 10.1039/c9cy00954j