Structure-Activity Relationships of Hydrothermally Aged Titania-Supported Vanadium-Tungsten Oxide Catalysts for SCR of NOx Emissions with NH3

Lai, Jun-Kun; Jaegers, Nicholas R.; Mosevitzky Lis, Bar; Guo, Mingyu; Ford, Michael E.; Walter, Eric D.; Wang, Yong; Hu, Jian Z.; Wachs, Israel

doi:10.1021/acscatal.1c02130

Title: Structure-Activity Relationships of Hydrothermally Aged Titania-Supported Vanadium-Tungsten Oxide Catalysts for SCR of NOx Emissions with NH3

Journal Article · Fri Oct 01 00:00:00 EDT 2021 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.1c02130· OSTI ID:1829450

Lai, Jun-Kun ^[1]; Jaegers, Nicholas R. ^[2]; Mosevitzky Lis, Bar ^[1]; Guo, Mingyu ^[1]; Ford, Michael E. ^[1];

^[2]; Wang, Yong ^[2];

^[2]; Wachs, Israel ^[1]

Lehigh University
BATTELLE (PACIFIC NW LAB)

Supported V2O5-WO3/TiO2 materials employed as selective catalytic reduction (SCR) catalysts for NOx emission control from power plants. Fresh SCR catalysts usually receive exposure to harsh treatments in industry to accelerate catalyst activation (calcination in air at 650oC) and catalyst aging (hydrothermal aging at 650oC) in a way that represents various points in the catalyst/product lifetime. The present study investigates the catalyst structural and chemical changes occurring during such harsh treatments. Three series of supported V2O5-WO3/TiO2 catalysts were prepared by incipient-wetness impregnation of aqueous ammonium metavanadate and metatungstate precursors. The catalysts were subsequently dried and calcined at 550oC in O2, 650oC in O2, and hydrothermal conditions (10% O2, 8% H2O, 7% CO2 and 75% N2) at 650oC. The resulting catalysts were physically characterized by numerous techniques (in situ Raman, in situ IR, in situ High Field-High Spinning solid-state 51V MAS NMR, in situ EPR, XRD, BET surface area and ICP) and chemically probed with adsorbed ammonia, SCR-TPSR, and the SCR reaction. The surface WOx sites on the TiO2 support behave as a textural promoter that stabilizes the TiO2 (anatase) phase from sintering and transforming to the undesirable crystalline TiO2 (rutile) phase that can lead to formation of a Ti1-xVxO2 (rutile) solid solution with reduced V4+ cations (~7-15%). The surface VOx sites are mostly oligomerized as surface V+5Ox sites (~50-85% oligomers) and the extent of oligomerization tends to increase with surface WOx coverage and calcination temperature. A major difference between the calcined and hydrothermally treated catalysts was the low concentration of surface NH3* species on Lewis acid sites for the hydrothermally treated catalysts, yet the SCR activity was almost comparable for both catalysts. This finding suggests that surface NH4+*, primarily associated with the surface VOx sites, are able to efficiently perform the SCR reaction. Given that multiple catalyst parameters were simultaneously varying during these treatments, it was difficult to correlate the SCR activity with any single catalyst parameter. A correlation, however, was found between the SCR TOF/activity and the sum of the surface NH3* and NH4+* species, which is dominated by the surface NH4+* species.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1829450

Report Number(s):: PNNL-SA-158279

Journal Information:: ACS Catalysis, Vol. 11, Issue 19

Country of Publication:: United States

Language:: English

References (48)

Reactivity of V2O5-WO3/TiO2 catalysts in the selective catalytic reduction of nitric oxide by ammonia Lietti, L.; Alemany, J. L.; Forzatti, P. Catalysis Today, Vol. 29, Issue 1-4 https://doi.org/10.1016/0920-5861(95)00250-2	journal	May 1996
Structural determination of supported vanadium pentoxide-tungsten trioxide-titania catalysts by in situ Raman spectroscopy and x-ray photoelectron spectroscopy Vuurman, Michael A.; Wachs, Israel E.; Hirt, Andrew M. The Journal of Physical Chemistry, Vol. 95, Issue 24 https://doi.org/10.1021/j100177a059	journal	November 1991
Selective Catalytic Reduction of NO with NH3over Supported Vanadia Catalysts Wachs, Israel E.; Deo, Goutam; Weckhuysen, Bert M. Journal of Catalysis, Vol. 161, Issue 1 https://doi.org/10.1006/jcat.1996.0179	journal	June 1996
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 Jaegers, Nicholas R.; Lai, Jun‐Kun; He, Yang Angewandte Chemie International Edition, Vol. 58, Issue 36 https://doi.org/10.1002/anie.201904503	journal	September 2019
A Perspective on the Selective Catalytic Reduction (SCR) of NO with NH ₃ by Supported V ₂ O ₅ –WO ₃ /TiO ₂ Catalysts Lai, Jun-Kun; Wachs, Israel E. ACS Catalysis, Vol. 8, Issue 7 https://doi.org/10.1021/acscatal.8b01357	journal	May 2018
Selective Catalytic Reduction of NO with NH3 on SO−24/TiO2 Superacid Catalyst Chen, J. P.; Yang, R. T. Journal of Catalysis, Vol. 139, Issue 1 https://doi.org/10.1006/jcat.1993.1023	journal	January 1993
Catalysis science of supported vanadium oxide catalysts Wachs, Israel E. Dalton Transactions, Vol. 42, Issue 33 https://doi.org/10.1039/c3dt50692d	journal	January 2013
Influence of catalyst synthesis method on selective catalytic reduction (SCR) of NO by NH3 with V2O5-WO3/TiO2 catalysts He, Yuanyuan; Ford, Michael E.; Zhu, Minghui Applied Catalysis B: Environmental, Vol. 193 https://doi.org/10.1016/j.apcatb.2016.04.022	journal	September 2016
Quantitative Determination of the Speciation of Surface Vanadium Oxides and Their Catalytic Activity Tian, Hanjing; Ross, Elizabeth I.; Wachs, Israel E. The Journal of Physical Chemistry B, Vol. 110, Issue 19 https://doi.org/10.1021/jp055767y	journal	May 2006
NOx Adsorber Aging on a Heavy-Duty On-Highway Diesel Engine - Part One Schenk, Charles; Laroo, Christopher SAE 2003 World Congress & Exhibition, SAE Technical Paper Series https://doi.org/10.4271/2003-01-0042	conference	March 2003
Lean and rich aging of a Cu/SSZ-13 catalyst for combined lean NO _x trap (LNT) and selective catalytic reduction (SCR) concept Auvray, Xavier; Grant, Ann; Lundberg, Björn Catalysis Science & Technology, Vol. 9, Issue 9 https://doi.org/10.1039/c8cy02572j	journal	January 2019
Comparison of Diesel Oxidation Catalyst Performance on an Engine and a Gas Flow Reactor Knafl, Alexander; Han, Manbae; Bohac, Stanislav V. SAE World Congress & Exhibition, SAE Technical Paper Series https://doi.org/10.4271/2007-01-0231	conference	April 2007
Overview of the practically important behaviors of zeolite-based urea-SCR catalysts, using compact experimental protocol Kamasamudram, Krishna; Currier, Neal W.; Chen, Xu Catalysis Today, Vol. 151, Issue 3-4 https://doi.org/10.1016/j.cattod.2010.03.055	journal	June 2010
Thermal activation and aging of a V2O5/WO3-TiO2 catalyst for the selective catalytic reduction of NO with NH3 Marberger, Adrian; Elsener, Martin; Nuguid, Rob Jeremiah G. Applied Catalysis A: General, Vol. 573 https://doi.org/10.1016/j.apcata.2019.01.009	journal	March 2019
VOx Surface Coverage Optimization of V2O5/WO3-TiO2 SCR Catalysts by Variation of the V Loading and by Aging Marberger, Adrian; Elsener, Martin; Ferri, Davide Catalysts, Vol. 5, Issue 4 https://doi.org/10.3390/catal5041704	journal	October 2015
Modeling Study of Urea SCR Catalyst Aging Characteristics Kim, Jeong Y.; Cheng, Yisun; Patterson, Joseph E. SAE World Congress & Exhibition, SAE Technical Paper Series https://doi.org/10.4271/2007-01-1580	conference	April 2007
Thermally Durable Vanadium-SCR Catalysts for Diesel Applications Maunula, Teuvo; Kinnunen, Toni; Kanniainen, Kauko SAE 2013 World Congress & Exhibition, SAE Technical Paper Series https://doi.org/10.4271/2013-01-1063	conference	April 2013
Technical Advantages of Vanadium SCR Systems for Diesel NOx Control in Emerging Markets Girard, James W.; Montreuil, Clifford; Kim, Jeong SAE International Journal of Fuels and Lubricants, Vol. 1, Issue 1 https://doi.org/10.4271/2008-01-1029	journal	April 2008
New Titania Materials with Improved Stability and Activity for Vanadia-Based Selective Catalytic Reduction of NOx Chapman, David Monroe; Fu, Guoyi; Augustine, Steve SAE International Journal of Fuels and Lubricants, Vol. 3, Issue 1 https://doi.org/10.4271/2010-01-1179	journal	April 2010
Evaluation of Hydrothermally Aged Vanadia SCR on High-Porosity Substrate Asako, Tsuyoshi; Kai, Ryuji; Toyoshima, Tetsuo SAE 2016 International Powertrains, Fuels & Lubricants Meeting, SAE Technical Paper Series https://doi.org/10.4271/2016-01-2320	conference	October 2016
Design and Durability of Vanadium-SCR Catalyst Systems in Mobile Off-Road Applications Maunula, Teuvo; Kinnunen, Toni; Iivonen, Markus SAE 2011 World Congress & Exhibition, SAE Technical Paper Series https://doi.org/10.4271/2011-01-1316	conference	April 2011
Design and Durability of Vanadium-SCR Catalytic Aftertreatment System to Meet Tier 4 Emission Regulations in a Locomotive Application Kababji, Alaa; Abhyankar, Atul; Li, Huiling Automotive Technical Papers, SAE Technical Paper Series https://doi.org/10.4271/2019-01-5015	conference	February 2019
Design of Durable Vanadium - SCR Catalyst Systems for Heavy - Duty Diesel Applications Maunula, Teuvo; Viitanen, Arto; Kinnunen, Toni Symposium on International Automotive Technology 2013, SAE Technical Paper Series https://doi.org/10.4271/2013-26-0049	conference	January 2013
The Significance of Lewis Acid Sites for the Selective Catalytic Reduction of Nitric Oxide on Vanadium-Based Catalysts Marberger, Adrian; Ferri, Davide; Elsener, Martin Angewandte Chemie International Edition, Vol. 55, Issue 39 https://doi.org/10.1002/anie.201605397	journal	August 2016
Studies of heterogeneous oxidation catalysts. Part 1.—The vanadium(V) oxide + titanium(IV) oxide system Cole, David J.; Cullis, Charles F.; Hucknall, David J. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 72, Issue 0 https://doi.org/10.1039/f19767202185	journal	January 1976
Kinetic parameter estimation for a multiresponse nonlinear reaction model Routray, Kamalakanta; Deo, Goutam AIChE Journal, Vol. 51, Issue 6 https://doi.org/10.1002/aic.10446	journal	January 2005
Phase sensitivity of Raman spectroscopy analysis of CVD titania thin films Lu, Song Wei; Harris, Caroline; Walck, Scott Journal of Materials Science, Vol. 44, Issue 2 https://doi.org/10.1007/s10853-008-3086-z	journal	January 2009
Raman spectra of titanium dioxide Balachandran, U.; Eror, N. G. Journal of Solid State Chemistry, Vol. 42, Issue 3 https://doi.org/10.1016/0022-4596(82)90006-8	journal	May 1982
Structural Determination of Bulk and Surface Tungsten Oxides with UV−vis Diffuse Reflectance Spectroscopy and Raman Spectroscopy Ross-Medgaarden, Elizabeth I.; Wachs, Israel E. The Journal of Physical Chemistry C, Vol. 111, Issue 41 https://doi.org/10.1021/jp074219c	journal	September 2007
Vibrational spectra of alumina- and silica-supported vanadia revisited: An experimental and theoretical model catalyst study Magg, N. Journal of Catalysis, Vol. 226, Issue 1 https://doi.org/10.1016/j.jcat.2004.04.021	journal	August 2004
Resolving the Atomic Structure of Vanadia Monolayer Catalysts: Monomers, Trimers, and Oligomers on Ceria Baron, Martin; Abbott, Heather; Bondarchuk, Oleksandr Angewandte Chemie International Edition, Vol. 48, Issue 43 https://doi.org/10.1002/anie.200903085	journal	October 2009
Anomalous reactivity of supported V2O5 nanoparticles for propane oxidative dehydrogenation: influence of the vanadium oxide precursor Carrero, Carlos A.; Keturakis, Christopher J.; Orrego, Andres Dalton Transactions, Vol. 42, Issue 35 https://doi.org/10.1039/c3dt50611h	journal	January 2013
Investigation of the Structure and Active Sites of TiO ₂ Nanorod Supported VO _x Catalysts by High-Field and Fast-Spinning ⁵¹ V MAS NMR Hu, Jian Zhi; Xu, Suochang; Li, Wei-Zhen ACS Catalysis, Vol. 5, Issue 7 https://doi.org/10.1021/acscatal.5b00286	journal	June 2015
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 Zhu, Minghui; Lai, Jun-Kun; Tumuluri, Uma Journal of the American Chemical Society, Vol. 139, Issue 44 https://doi.org/10.1021/jacs.7b09646	journal	October 2017
Metals emitted from heavy-duty diesel vehicles equipped with advanced PM and NOX emission controls Hu, Shaohua; Herner, Jorn D.; Shafer, Martin Atmospheric Environment, Vol. 43, Issue 18 https://doi.org/10.1016/j.atmosenv.2009.02.052	journal	June 2009
Methods for Quantifying the Release of Vanadium from Engine Exhaust Aftertreatment Catalysts Liu, Z. Gerald; Ottinger, Nathan A.; Cremeens, Christopher M. SAE International Journal of Engines, Vol. 5, Issue 2 https://doi.org/10.4271/2012-01-0887	journal	January 2012
Vanadium and tungsten release from V-based selective catalytic reduction diesel aftertreatment Liu, Z. Gerald; Ottinger, Nathan A.; Cremeens, Christopher M. Atmospheric Environment, Vol. 104 https://doi.org/10.1016/j.atmosenv.2014.12.063	journal	March 2015
Vanadium-Based SCR Systems: Release of Vanadium and Tungsten during Operation and Possibilities for Reducing Vanadium Emissions Hoej, Jakob; Beier, Matthias Josef SAE International Journal of Engines, Vol. 7, Issue 3 https://doi.org/10.4271/2014-01-1626	journal	April 2014
Surface characterization studies on F-doped V2O5/TiO2 catalyst for NO reduction with NH3 at low-temperature Zhang, Shule; Zhong, Qin; Zhao, Wei Chemical Engineering Journal, Vol. 253 https://doi.org/10.1016/j.cej.2014.04.045	journal	October 2014
A new view on the relations between tungsten and vanadium in V2O5WO3/TiO2 catalysts for the selective reduction of NO with NH3 Kompio, Patrick G. W. A.; Brückner, Angelika; Hipler, Frank Journal of Catalysis, Vol. 286 https://doi.org/10.1016/j.jcat.2011.11.008	journal	February 2012
Studies of heterogeneous oxidation catalysts. Part 2.—The vanadium (V) oxide + molybdenum (VI) oxide and other binary oxide systems Cole, David J.; Cullis, Charles F.; Hucknall, David J. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 72, Issue 0 https://doi.org/10.1039/f19767202744	journal	January 1976
Effect of Milling of V ₂ O ₅ on the Local Environment of Vanadium as Studied by Solid-State ⁵¹ V NMR and Complementary Methods Shubin, A. A.; Lapina, O. B.; Bosch, E. The Journal of Physical Chemistry B, Vol. 103, Issue 16 https://doi.org/10.1021/jp984513s	journal	April 1999
Characterization of V ₂ O ₅ −TiO ₂ Catalysts Prepared by Milling by ESR and Solid State ¹ H and ⁵¹ V NMR Lapina, Olga B.; Shubin, Alexander A.; Nosov, Andrei V. The Journal of Physical Chemistry B, Vol. 103, Issue 36 https://doi.org/10.1021/jp991405c	journal	August 1999
Transient operando study on the NH3/NH4+ interplay in V-SCR monolithic catalysts Rasmussen, Søren B.; Portela, Raquel; Bazin, Philippe Applied Catalysis B: Environmental, Vol. 224 https://doi.org/10.1016/j.apcatb.2017.10.026	journal	May 2018
Selective catalytic reduction of NO by NH3 with WO3-TiO2 catalysts: Influence of catalyst synthesis method He, Yuanyuan; Ford, Michael E.; Zhu, Minghui Applied Catalysis B: Environmental, Vol. 188 https://doi.org/10.1016/j.apcatb.2016.01.072	journal	July 2016
Chemical and mechanistic aspects of the selective catalytic reduction of NO by ammonia over oxide catalysts: A review Busca, Guido; Lietti, Luca; Ramis, Gianguido Applied Catalysis B: Environmental, Vol. 18, Issue 1-2 https://doi.org/10.1016/s0926-3373(98)00040-x	journal	September 1998
Vanadia/Titania Catalysts for Selective Catalytic Reduction (SCR) of Nitric-Oxide by Ammonia Topsoe, N. Y.; Topsoe, H.; Dumesic, J. A. Journal of Catalysis, Vol. 151, Issue 1 https://doi.org/10.1006/jcat.1995.1024	journal	January 1995
Vanadia-Titania Catalysts for Selective Catalytic Reduction of Nitric-Oxide by Ammonia Topsoe, N. Y.; Dumesic, J. A.; Topsoe, H. Journal of Catalysis, Vol. 151, Issue 1 https://doi.org/10.1006/jcat.1995.1025	journal	January 1995

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Title: Structure-Activity Relationships of Hydrothermally Aged Titania-Supported Vanadium-Tungsten Oxide Catalysts for SCR of NOx Emissions with NH3

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