Dual aging pathways of Cu-SSZ-13 SCR catalysts: Hydrothermal vs. sulfur-induced deactivation

Deka, Dhruba Jyoti; Andana, Tahrizi; Daya, Rohil; Gao, Feng; Walter, Eric D.; Hu, Jian Zhi; Lee, Garam; Bowden, Mark E.; Wang, Yong; Rappe, Kenneth G.

doi:10.1016/j.cej.2025.171436

Dual aging pathways of Cu-SSZ-13 SCR catalysts: Hydrothermal vs. sulfur-induced deactivation

Journal Article · Tue Dec 02 00:00:00 EST 2025 · Chemical Engineering Journal

DOI:https://doi.org/10.1016/j.cej.2025.171436· OSTI ID:3010927

Deka, Dhruba Jyoti ^[1]; Andana, Tahrizi ^[2]; Daya, Rohil ^[3]; ^[1]; ^[1]; Hu, Jian Zhi ^[4]; Lee, Garam ^[1]; Bowden, Mark E. ^[1]; Wang, Yong ^[4]; ^[1]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Cummins Emission Solutions, Stoughton, WI (United States)
Cummins Inc., Columbus, IN (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)

Hydrothermal aging (HTA) and chemical poisoning are two primary factors contributing to the real-world degradation of Cu-SSZ-13 SCR catalysts. Investigating field-returned samples offers valuable insights into performance degradation caused by these mechanisms. However, the simultaneous presence of both deactivation pathways complicates the isolation of their individual effects in post-mortem analyses. In this study, we separately prepared model Cu-SSZ-13 SCR catalysts subjected to hydrothermal-aging and sulfur-induced chemical poisoning. Using various characterization techniques, we elucidated the specific role of each aging process in catalyst deactivation and compared the results to real-world field-aged catalysts. Our findings show that hydrothermal aging at 650 °C for 100 h caused dealumination of the zeolite framework but no significant CuO_x cluster formation. In contrast, sulfur aging (via sulfur exposure, calcination at 550 °C, and desulfation up to 750 °C) led to CuO_x formation without any observable dealumination. On model catalysts, sulfur poisoning was found to reduce Cu mobility and the amount of active Cu sites, thus degrading catalyst activity. Although some activity was recovered upon desulfation, a portion of the initial catalyst activity remained irreversibly lost due to CuO_x formation. We demonstrate that this occurs because sulfated species impede the ability of multi-nuclear Cu species (e.g., Cu dimers) to split back into their isolated form, leading to CuSO₄-clusters that oxidatively desulfate to CuO_x species. This degradation pathway explains the significant reduction in activity of field-aged samples, where substantial CuSO₄-cluster accumulation leads to reduced active Cu and subsequent conversion to CuO_x. Furthermore, the conclusions from model catalysts were extended directly to field-aged commercial samples, elucidating the decline in activity and chemical properties during field deployment.

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), 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:: 3010927

Report Number(s):: PNNL-SA--208507

Journal Information:: Chemical Engineering Journal, Journal Name: Chemical Engineering Journal Vol. 526; ISSN 1385-8947

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Catalyst Deactivation
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Dual aging pathways of Cu-SSZ-13 SCR catalysts: Hydrothermal vs. sulfur-induced deactivation

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