A comparative study between real-world and laboratory accelerated aging of Cu/SSZ-13 SCR catalysts

Wu, Yiqing; Andana, Tahrizi; Wang, Yilin; Chen, Ying; Walter, Eric D.; Engelhard, Mark H.; Rappé, Kenneth G.; Wang, Yong; Gao, Feng; Menon, Unmesh; Daya, Rohil; Trandal, Dylan; An, Hongmei; Zha, Yuhui; Kamasamudram, Krishna

doi:10.1016/j.apcatb.2022.121807

A comparative study between real-world and laboratory accelerated aging of Cu/SSZ-13 SCR catalysts

Journal Article · Wed Aug 03 00:00:00 EDT 2022 · Applied Catalysis. B, Environmental

DOI:https://doi.org/10.1016/j.apcatb.2022.121807· OSTI ID:2340096

Wu, Yiqing ^[1]; Andana, Tahrizi ^[1]; Wang, Yilin ^[1]; Chen, Ying ^[1]; Walter, Eric D. ^[1]; Engelhard, Mark H. ^[1]; Rappé, Kenneth G. ^[1]; Wang, Yong ^[1]; Gao, Feng ^[1]; Menon, Unmesh ^[2]; Daya, Rohil ^[2]; Trandal, Dylan ^[2]; An, Hongmei ^[2]; Zha, Yuhui ^[2]; Kamasamudram, Krishna ^[2]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Cummins, Columbus, IN (United States)

Elucidating aging mechanisms in real-world applications is a critical component for developing and maintaining Cu/SSZ-13 SCR catalysts. To reveal gaps between laboratory accelerated aging and real-world aging, herein we report thorough comparative studies between 6 representative catalysts. Here, we apply a wide range of catalyst characterization methods, including surface area/porosity analysis, X-ray diffraction (XRD), H₂-temperature programmed reduction, NH3-temperaure programmed desorption, solid-state nuclear magnetic resonance (NMR), in situ X-ray photoelectron (XPS) and electron paramagnetic resonance (EPR) spectroscopies, to gain atomic-level knowledge on Cu transformation under different aging protocols. We then correlate such knowledge to SCR, NH₃/NO oxidation kinetic behavior of the catalysts. We found that sulfur aging plays the most important role in interpreting catalyst degradation during real-world application, including direct sulfur poisoning of isolated Cu^II SCR active species to CuSO₄-like species, the agglomeration of such species to multinuclear CuSO₄ clusters, and eventually, CuO formation during desulfation treatments. Such chemistries convert SCR active Cu to SCR inert Cu moieties without severely deteriorating catalyst support integrity. These characteristics are partially replicated by hydrothermal aging in the presence of SOx but are poorly mimicked by hydrothermal aging alone.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2340096

Alternate ID(s):: OSTI ID: 1880172

Report Number(s):: PNNL-SA--172435

Journal Information:: Applied Catalysis. B, Environmental, Journal Name: Applied Catalysis. B, Environmental Vol. 318; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (64)

Site-Specific Reactivity of Copper Chabazite Zeolites with Nitric Oxide, Ammonia, and Oxygen Godiksen, Anita; Isaksen, Oliver L.; Rasmussen, Søren B. ChemCatChem, Vol. 10, Issue 2 https://doi.org/10.1002/cctc.201701357	journal	November 2017
Kinetics of thermal decomposition of CuSO ₄ · 5H ₂ O to CuO: THERMAL DECOMPOSITION OF CuSO ₄ ·5H ₂ O TO CuO Gadalla, Ahmed M. International Journal of Chemical Kinetics, Vol. 16, Issue 6 https://doi.org/10.1002/kin.550160604	journal	June 1984
Modeling of EPR Parameters for Cu(II): Application to the Selective Reduction of NOx Catalyzed by Cu-Zeolites Fernández, Estefanía; Moreno-González, Marta; Moliner, Manuel Topics in Catalysis, Vol. 61, Issue 9-11 https://doi.org/10.1007/s11244-018-0929-y	journal	April 2018
XPS study of clean metal sulfide surfaces Laajalehto, K.; Kartio, I.; Nowak, P. Applied Surface Science, Vol. 81, Issue 1 https://doi.org/10.1016/0169-4332(94)90080-9	journal	September 1994
The x-ray photoelectron spectra of metal complexes of sulfur-containing ligands: sulfur 2p binding energies Walton, R. A. Coordination Chemistry Reviews, Vol. 31, Issue 3 https://doi.org/10.1016/S0010-8545(00)80449-X	journal	April 1980
Kinetics of selective catalytic reduction of NO with NH3 on Fe-ZSM-5 catalyst Huang, H. Y.; Long, R. Q.; Yang, R. T. Applied Catalysis A: General, Vol. 235, Issue 1-2 https://doi.org/10.1016/S0926-860X(02)00268-5	journal	August 2002
On the hydrothermal stability of Cu/SSZ-13 SCR catalysts Gao, Feng; Szanyi, János Applied Catalysis A: General, Vol. 560 https://doi.org/10.1016/j.apcata.2018.04.040	journal	June 2018
Relationships between copper speciation and Brønsted acidity evolution over Cu-SSZ-13 during hydrothermal aging Ma, Yue; Wu, Xiaodong; Cheng, Songqi Applied Catalysis A: General, Vol. 602 https://doi.org/10.1016/j.apcata.2020.117650	journal	July 2020
The influence of silicon on the catalytic properties of Cu/SAPO-34 for NOx reduction by ammonia-SCR Wang, Jun; Yu, Tie; Wang, Xinquan Applied Catalysis B: Environmental, Vol. 127 https://doi.org/10.1016/j.apcatb.2012.08.016	journal	October 2012
Effect of gas compositions on SO2 poisoning over Cu/SSZ-13 used for NH3-SCR Wijayanti, Kurnia; Xie, Kunpeng; Kumar, Ashok Applied Catalysis B: Environmental, Vol. 219 https://doi.org/10.1016/j.apcatb.2017.07.017	journal	December 2017
Reversible and irreversible deactivation of Cu-CHA NH3-SCRcatalysts by SO2 and SO3 Hammershøi, Peter S.; Jangjou, Yasser; Epling, William S. Applied Catalysis B: Environmental, Vol. 226 https://doi.org/10.1016/j.apcatb.2017.12.018	journal	June 2018
Enhancement of high-temperature selectivity on Cu-SSZ-13 towards NH3-SCR reaction from highly dispersed ZrO2 Peng, Bo; Rappé, Kenneth G.; Cui, Yanran Applied Catalysis B: Environmental, Vol. 263 https://doi.org/10.1016/j.apcatb.2019.118359	journal	April 2020
Effects of hydrothermal aging on the sulfur poisoning of a Cu-SSZ-13 SCR catalyst Xi, Yuanzhou; Su, Changsheng; Ottinger, Nathan A. Applied Catalysis B: Environmental, Vol. 284 https://doi.org/10.1016/j.apcatb.2020.119749	journal	May 2021
Dynamics of low temperature N2O formation under SCR reaction conditions over a Cu-SSZ-13 catalyst Xi, Yuanzhou; Ottinger, Nathan A.; Keturakis, Christopher J. Applied Catalysis B: Environmental, Vol. 294 https://doi.org/10.1016/j.apcatb.2021.120245	journal	October 2021
Regeneration of sulfur-poisoned Cu-SSZ-13 catalysts: Copper speciation and catalytic performance evaluation Mesilov, Vitaly; Dahlin, Sandra; Bergman, Susanna L. Applied Catalysis B: Environmental, Vol. 299 https://doi.org/10.1016/j.apcatb.2021.120626	journal	December 2021
Thermal durability of Cu-CHA NH3-SCR catalysts for diesel NOx reduction Schmieg, Steven J.; Oh, Se H.; Kim, Chang H. Catalysis Today, Vol. 184, Issue 1 https://doi.org/10.1016/j.cattod.2011.10.034	journal	April 2012
Impact of different forms of feed sulfur on small-pore Cu-zeolite SCR catalyst Kumar, Ashok; Smith, Michael A.; Kamasamudram, Krishna Catalysis Today, Vol. 231 https://doi.org/10.1016/j.cattod.2013.12.038	journal	August 2014
Identification of two types of Cu sites in Cu/SSZ-13 and their unique responses to hydrothermal aging and sulfur poisoning Luo, Jinyong; Wang, Di; Kumar, Ashok Catalysis Today, Vol. 267 https://doi.org/10.1016/j.cattod.2015.12.002	journal	June 2016
Chemical deSOx: An effective way to recover Cu-zeolite SCR catalysts from sulfur poisoning Kumar, Ashok; Smith, Michael A.; Kamasamudram, Krishna Catalysis Today, Vol. 267 https://doi.org/10.1016/j.cattod.2016.01.033	journal	June 2016
Chemical aging of Cu-SSZ-13 SCR catalysts for heavy-duty vehicles – Influence of sulfur dioxide Dahlin, Sandra; Lantto, Cornelia; Englund, Johanna Catalysis Today, Vol. 320 https://doi.org/10.1016/j.cattod.2018.01.035	journal	January 2019
Impact of low temperature sulfur exposure on the aging of small pore Cu-zeolite SCR catalyst Tang, Yadan; Wang, Di; Wang, Xiang Catalysis Today, Vol. 360 https://doi.org/10.1016/j.cattod.2020.04.033	journal	January 2021
Characterization of commercial Cu-SSZ-13 and Cu-SAPO-34 catalysts with hydrothermal treatment for NH3-SCR of NOx in diesel exhaust Ma, Lei; Cheng, Yisun; Cavataio, Giovanni Chemical Engineering Journal, Vol. 225 https://doi.org/10.1016/j.cej.2013.03.078	journal	June 2013
Steam and alkali resistant Cu-SSZ-13 catalyst for the selective catalytic reduction of NOx in diesel exhaust Fan, Chi; Chen, Zhen; Pang, Lei Chemical Engineering Journal, Vol. 334 https://doi.org/10.1016/j.cej.2017.09.181	journal	February 2018
Insight into the SO2 poisoning mechanism for NOx removal by NH3-SCR over Cu/LTA and Cu/SSZ-13 Wang, Aiyong; Olsson, Louise Chemical Engineering Journal, Vol. 395 https://doi.org/10.1016/j.cej.2020.125048	journal	September 2020
NH3-TPD methodology for quantifying hydrothermal aging of Cu/SSZ-13 SCR catalysts Luo, Jinyong; Kamasamudram, Krishna; Currier, Neal Chemical Engineering Science, Vol. 190 https://doi.org/10.1016/j.ces.2018.06.015	journal	November 2018
Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NOx with NH3 Kwak, Ja Hun; Tonkyn, Russell G.; Kim, Do Heui Journal of Catalysis, Vol. 275, Issue 2 https://doi.org/10.1016/j.jcat.2010.07.031	journal	October 2010
Effects of hydrothermal aging on NH3-SCR reaction over Cu/zeolites Kwak, Ja Hun; Tran, Diana; Burton, Sarah D. Journal of Catalysis, Vol. 287 https://doi.org/10.1016/j.jcat.2011.12.025	journal	March 2012
Structure–activity relationships in NH3-SCR over Cu-SSZ-13 as probed by reaction kinetics and EPR studies Gao, Feng; Walter, Eric D.; Karp, Eric M. Journal of Catalysis, Vol. 300 https://doi.org/10.1016/j.jcat.2012.12.020	journal	April 2013
Hydrothermal stability of CuSSZ13 for reducing NOx by NH3 Kim, Young Jin; Lee, Jun Kyu; Min, Kyung Myung Journal of Catalysis, Vol. 311 https://doi.org/10.1016/j.jcat.2013.12.012	journal	March 2014
NO oxidation: A probe reaction on Cu-SSZ-13 Verma, Anuj A.; Bates, Shane A.; Anggara, Trunojoyo Journal of Catalysis, Vol. 312 https://doi.org/10.1016/j.jcat.2014.01.017	journal	April 2014
Understanding ammonia selective catalytic reduction kinetics over Cu/SSZ-13 from motion of the Cu ions Gao, Feng; Walter, Eric D.; Kollar, Marton Journal of Catalysis, Vol. 319 https://doi.org/10.1016/j.jcat.2014.08.010	journal	November 2014
A comparative study of N2O formation during the selective catalytic reduction of NOx with NH3 on zeolite supported Cu catalysts Chen, Hai-Ying; Wei, Zhehao; Kollar, Marton Journal of Catalysis, Vol. 329 https://doi.org/10.1016/j.jcat.2015.06.016	journal	September 2015
Effects of Si/Al ratio on Cu/SSZ-13 NH3-SCR catalysts: Implications for the active Cu species and the roles of Brønsted acidity Gao, Feng; Washton, Nancy M.; Wang, Yilin Journal of Catalysis, Vol. 331 https://doi.org/10.1016/j.jcat.2015.08.004	journal	November 2015
New insights into Cu/SSZ-13 SCR catalyst acidity. Part I: Nature of acidic sites probed by NH3 titration Luo, Jinyong; Gao, Feng; Kamasamudram, Krishna Journal of Catalysis, Vol. 348 https://doi.org/10.1016/j.jcat.2017.02.025	journal	April 2017
Cu/Chabazite catalysts for ‘Lean-Burn’ vehicle emission control Peden, Charles H. F. Journal of Catalysis, Vol. 373 https://doi.org/10.1016/j.jcat.2019.04.046	journal	May 2019
Revisiting effects of alkali metal and alkaline earth co-cation additives to Cu/SSZ-13 selective catalytic reduction catalysts Cui, Yanran; Wang, Yilin; Mei, Donghai Journal of Catalysis, Vol. 378 https://doi.org/10.1016/j.jcat.2019.08.028	journal	October 2019
Solvation and Mobilization of Copper Active Sites in Zeolites by Ammonia: Consequences for the Catalytic Reduction of Nitrogen Oxides Paolucci, Christopher; Di Iorio, John R.; Schneider, William F. Accounts of Chemical Research, Vol. 53, Issue 9 https://doi.org/10.1021/acs.accounts.0c00328	journal	August 2020
Revealing the Synergistic Deactivation Mechanism of Hydrothermal Aging and SO ₂ Poisoning on Cu/SSZ-13 under SCR Condition Zhang, Yani; Zhu, Hongchang; Zhang, Tao Environmental Science & Technology, Vol. 56, Issue 3 https://doi.org/10.1021/acs.est.1c06068	journal	December 2021
Quantitative Cu Counting Methodologies for Cu/SSZ-13 Selective Catalytic Reduction Catalysts by Electron Paramagnetic Resonance Spectroscopy Zhang, Yani; Wu, Yiqing; Peng, Yue The Journal of Physical Chemistry C, Vol. 124, Issue 51 https://doi.org/10.1021/acs.jpcc.0c07971	journal	December 2020
Selective Catalytic Reduction of NO _x with NH ₃ over Cu/SSZ-13: Elucidating Dynamics of Cu Active Sites with In Situ UV–Vis Spectroscopy and DFT Calculations Zhang, Yani; Zhang, Jun; Wang, Houlin The Journal of Physical Chemistry C, Vol. 126, Issue 20 https://doi.org/10.1021/acs.jpcc.2c01268	journal	May 2022
Probing Active-Site Relocation in Cu/SSZ-13 SCR Catalysts during Hydrothermal Aging by In Situ EPR Spectroscopy, Kinetics Studies, and DFT Calculations Zhang, Yani; Peng, Yue; Li, Junhua ACS Catalysis, Vol. 10, Issue 16 https://doi.org/10.1021/acscatal.0c01590	journal	June 2020
Influence of ZCuOH, Z ₂ Cu, and Extraframework Cu _x O _y Species in Cu-SSZ-13 on N ₂ O Formation during the Selective Catalytic Reduction of NO _x with NH ₃ Shih, Arthur J.; González, Juan M.; Khurana, Ishant ACS Catalysis, Vol. 11, Issue 16 https://doi.org/10.1021/acscatal.1c01871	journal	August 2021
Unraveling the Hydrolysis of Z ₂ Cu ²⁺ to ZCu ²⁺ (OH) ⁻ and Its Consequences for the Low-Temperature Selective Catalytic Reduction of NO on Cu-CHA Catalysts Hu, Wenshuo; Iacobone, Umberto; Gramigni, Federica ACS Catalysis, Vol. 11, Issue 18 https://doi.org/10.1021/acscatal.1c02761	journal	September 2021
Effects of Alkali and Alkaline Earth Cocations on the Activity and Hydrothermal Stability of Cu/SSZ-13 NH ₃ –SCR Catalysts Gao, Feng; Wang, Yilin; Washton, Nancy M. ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b01621	journal	October 2015
Toward Rational Design of Cu/SSZ-13 Selective Catalytic Reduction Catalysts: Implications from Atomic-Level Understanding of Hydrothermal Stability Song, James; Wang, Yilin; Walter, Eric D. ACS Catalysis, Vol. 7, Issue 12 https://doi.org/10.1021/acscatal.7b03020	journal	November 2017
Nature of Cu Active Centers in Cu-SSZ-13 and Their Responses to SO ₂ Exposure Jangjou, Yasser; Do, Quan; Gu, Yuntao ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b03095	journal	January 2018
Catalysis in a Cage: Condition-Dependent Speciation and Dynamics of Exchanged Cu Cations in SSZ-13 Zeolites Paolucci, Christopher; Parekh, Atish A.; Khurana, Ishant Journal of the American Chemical Society, Vol. 138, Issue 18 https://doi.org/10.1021/jacs.6b02651	journal	April 2016
Selective Catalytic Reduction over Cu/SSZ-13: Linking Homo- and Heterogeneous Catalysis Gao, Feng; Mei, Donghai; Wang, Yilin Journal of the American Chemical Society, Vol. 139, Issue 13 https://doi.org/10.1021/jacs.7b01128	journal	March 2017
Coordination Environment of Copper Sites in Cu-CHA Zeolite Investigated by Electron Paramagnetic Resonance Godiksen, Anita; Stappen, Frederick N.; Vennestrøm, Peter N. R. The Journal of Physical Chemistry C, Vol. 118, Issue 40 https://doi.org/10.1021/jp5065616	journal	September 2014
Correlation of Relative X-ray Photoelectron Spectroscopy Shake-up Intensity with CuO Particle Size Chusuei, C. C.; Brookshier, M. A.; Goodman, D. W. Langmuir, Vol. 15, Issue 8 https://doi.org/10.1021/la9815446	journal	April 1999
Ammonia selective catalytic reduction of NO over Fe/Cu-SSZ-13 Zhang, Ranran; Li, Yonghong; Zhen, Tieli RSC Adv., Vol. 4, Issue 94 https://doi.org/10.1039/C4RA09290B	journal	January 2014
Recent advances in automotive catalysis for NO _x emission control by small-pore microporous materials Beale, A. M.; Gao, F.; Lezcano-Gonzalez, I. Chemical Society Reviews, Vol. 44, Issue 20 https://doi.org/10.1039/C5CS00108K	journal	January 2015
Principles and applications of EPR spectroscopy in the chemical sciences Roessler, Maxie M.; Salvadori, Enrico Chemical Society Reviews, Vol. 47, Issue 8 https://doi.org/10.1039/C6CS00565A	journal	January 2018
Identification of sulfate species and their influence on SCR performance of Cu/CHA catalyst Su, Wenkang; Li, Zhenguo; Zhang, Yani Catalysis Science & Technology, Vol. 7, Issue 7 https://doi.org/10.1039/C7CY00302A	journal	January 2017
Site selective adsorption and relocation of SO _x in deactivation of Cu–CHA catalysts for NH ₃ -SCR Hammershøi, Peter S.; Godiksen, Anita L.; Mossin, Susanne Reaction Chemistry & Engineering, Vol. 4, Issue 6 https://doi.org/10.1039/C8RE00275D	journal	January 2019
Alternate pathway for standard SCR on Cu-zeolites with gas-phase ammonia Daya, Rohil; Keturakis, Christopher J.; Trandal, Dylan Reaction Chemistry & Engineering, Vol. 6, Issue 6 https://doi.org/10.1039/D1RE00041A	journal	January 2021
CuO by XPS Vasquez, R. P. Surface Science Spectra, Vol. 5, Issue 4 https://doi.org/10.1116/1.1247882	journal	October 1998
CuSO4 by XPS Vasquez, R. P. Surface Science Spectra, Vol. 5, Issue 4 https://doi.org/10.1116/1.1247885	journal	October 1998
Nature of the use of adventitious carbon as a binding energy standard Barr, Tery L.; Seal, Sudipta Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 13, Issue 3 https://doi.org/10.1116/1.579868	journal	May 1995
Dynamic multinuclear sites formed by mobilized copper ions in NO _x selective catalytic reduction Paolucci, Christopher; Khurana, Ishant; Parekh, Atish A. Science, Vol. 357, Issue 6354 https://doi.org/10.1126/science.aan5630	journal	August 2017
Hydrocarbon Storage on Small-Pore Cu-Zeolite SCR Catalyst Kumar, Ashok; Kamasamudram, Krishna; Yezerets, Aleksey SAE International Journal of Engines, Vol. 6, Issue 2 https://doi.org/10.4271/2013-01-0508	journal	April 2013
Impact of Accelerated Hydrothermal Aging on Structure and Performance of Cu-SSZ-13 SCR Catalysts Luo, Jinyong; An, Hongmei; Kamasamudram, Krishna SAE International Journal of Engines, Vol. 8, Issue 3 https://doi.org/10.4271/2015-01-1022	journal	January 2015
Effect of Transition Metal Ion Properties on the Catalytic Functions and Sulfation Behavior of Zeolite-Based SCR Catalysts Kumar, Ashok; Kamasamudram, Krishna; Currier, Neal SAE International Journal of Engines, Vol. 10, Issue 4 https://doi.org/10.4271/2017-01-0939	journal	February 2017
Sulfur Poisoning of a Cu-SSZ-13 SCR Catalyst under Simulated Diesel Engine Operating Conditions Xi, Yuanzhou; Ottinger, Nathan; Su, Changsheng SAE International Journal of Advances and Current Practices in Mobility, Vol. 3, Issue 5 https://doi.org/10.4271/2021-01-0576	journal	April 2021