Fundamental insight into copper-based zeolite catalysts for NH3-SCR: Two decades’ progress and future perspectives

doi:10.1016/S1872-2067(26)65136-4

Chinese Journal of Catalysis ›› 2026, Vol. 89: 76-101.DOI: 10.1016/S1872-2067(26)65136-4

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Fundamental insight into copper-based zeolite catalysts for NH₃-SCR: Two decades’ progress and future perspectives

Ruiyuan Liu^a, Chengyang Yin^b, Chengming Zhong^a^,^*(), Jia Hou^a, Xiaofei Song^a, Jian Liu^a, Zhen Zhao^a^,^b^,^*()

^aState Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China
^bInstitute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, Liaoning, China

Received:2025-12-28 Accepted:2026-02-14 Online:2026-10-18 Published:2026-09-01
Contact: *E-mail:zhongchengming2022@126.com(C. Zhong),zhenzhao@cup.edu.cn/zhaozhen1586@163.com(Z. Zhao).
About author:Chengming Zhong (College of Science & State Key Laboratory of Heavy Oil Processing, China University of Petroleum-Beijing) He received his M.S. degree from China University of Petroleum-Beijing in 2020. Since 2020, he has been pursuing his Ph.D. degree at China University of Petroleum-Beijing. His research interests are focused on catalyst design and catalysis nature study for environmental catalysis, especially for vehicle exhaust emission control and industrial flue gas emission control from non-electric industries. He has published 2 peer-reviewed papers and been granted 1 authorized invention patent.
Zhen Zhao (College of Chemistry and Chemical Engineering, Shenyang Normal University) received his Ph.D. degree in 1996 from Changchun Institute of Applied Chemistry, Chinese Academy of Sciences. From 1997 to 2002, he conducted postdoctoral research at National Institute for Resources and Environment (AIST, Japan), National Institute of Industrial Technology (Osaka, Japan), and Lehigh University (USA). Now, he is a Distinguished Professor “Changjiang Scholars Program”, Second Class Professor and Doctoral Supervisor at China University of Petroleum (Beijing); Shenyang Normal University Special Professor Hired, Dean of the College of Chemistry and Chemical Engineering at Shenyang Normal University, and Director of Institute of Catalysis for Energy and Environment. His research interests are focused on catalyst design and catalysis nature study for the energy catalysis; environmental catalysis and rare earth catalysis, especially for diesel exhaust purification, petrochemical conversion of oil and gas, and CO₂ conversion and utilization. He has published more than 600 peer-reviewed papers with over 26800 citations and an H-index of 85, and has been an Elsevier Highly Cited Chinese Researcher for 11 consecutive years with more than 60 authorized invention patents.
Supported by:
National Natural Science Foundation of China(U25A20557);National Natural Science Foundation of China(22572131);National Key R&D Program of China(2021YFB3500601);National Key R&D Program of China(2021YFB3500603);National Key R&D Program of China(2022YFB3504100)

Abstract

Abstract:

Amidst tightening mobile-source emission regulations, ammonia selective catalytic reduction remains the dominant post-treatment technology for NO_x removal, with copper-exchanged zeolites (Cu-zeolites) serving as benchmark catalysts. Here, we systematically survey zeolite topologies—such as MFI, CHA, AEI, and LTA—evaluating their catalytic performance, reaction mechanisms, hydrothermal stability, and resistance to poisoning. A comprehensive overall pathway of sequential two-NO activation on dual ZCuOH sites is unified and complements the established L-NH₃ (NH₃ bond to solvated Cu²⁺ ions) activation model in the Reduction Half-Cycle. This work provides fundamental insights into the performance, hydrothermal stability, and SO₂ resistance of Cu-based zeolites. Therefore, the fundamentals and new mechanistic insights of hydrothermal aging are summarized over Cu-SSZ-13, while highlighting Cu-SSZ-39 as an intrinsically robust successor. We dissect the SO₂ poisoning mechanisms of Cu-CHA, demonstrating that engineering the atomic-scale distribution of Cu enhances both sulfur tolerance and hydrothermal stability. Supplementary strategies (e.g., constructing protective/sacrificial sites, co-crystallization, and core-shell structures) are also considered beneficial. Beyond durability, we also focus on the two-dimensional PST-9 zeolite and OFF/ERI intergrowths zeolite for the future challenge of diffusion. Finally, we outline future research frontiers, aiming to unify Cu-zeolite theory into a mechanistic framework that translates fundamental insights into rational design principles for next-generation catalysts.

Key words: Cu-zeolites, Ammonia selective catalytic reduction, Reaction mechanism, Hydrothermal stability, Sulfur tolerance

Ruiyuan Liu, Chengyang Yin, Chengming Zhong, Jia Hou, Xiaofei Song, Jian Liu, Zhen Zhao. Fundamental insight into copper-based zeolite catalysts for NH₃-SCR: Two decades’ progress and future perspectives[J]. Chinese Journal of Catalysis, 2026, 89: 76-101.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65136-4

https://www.cjcatal.com/EN/Y2026/V89/I10/76

Figures/Tables 27

Fig. 1. The contents of this paper.

Fig. 2. Low temperature NH3-SCR reaction mechanisms and strategies for diffusion limitation, hydrothermal stability, and SO2 resistance of Cu based zeolite.

Table 1 The range of activity prepared by different methods (ZSM-5).

Catalyst	Active range	Preparation method	Conditions	Ref.
3.5Cu/0.6NaZSM-5	220-400 °C (T₈₀)	Ion exchange method	200 ppm NO, 200 ppm NH₃, 10% O₂, 6% H₂O, GHSV = 125000 h^-1	[52]
Cu-ZSM-5-ZrO₂	210-400 °C (T₈₀)	Ion exchange method	500ppm NO, 500 ppm NH₃, 10% O₂, 1.5% H₂O, GHSV = 28000 h^-1	[53]
CuCe/ZSM-5	250-400 °C (T₉₀)	Impregnation method	1000 ppm NO, 1100 ppm NH₃, 5% O_2，10% H₂O, GHSV = 30000 h^-1	[54]
Ce₁-Cu₄/ZSM-5	185-470 °C (T₉₀)	Impregnation method	500 ppm NO, 500 ppm NH₃, 5% O₂, GHSV = 55000 h^-1	[55]
Cu-Zr/ZSM-5	167-452 °C (T₉₅)	Ion exchange method	1000 ppm NO, 1000 ppm NH₃, 10% O₂, GHSV = 100000 h^-1	[56]
CuCe_0.75Zr_0.25/ZSM-5	175-468 °C (T₉₅)	Ion exchange method	1000 ppm NO, 1000 ppm NH₃, 10% O₂, GHSV = 15000 h^-1	[57]
NS_L-Cu-ZSM-5	250-550 °C (T₁₀₀)	Ion exchange method	1000 ppm NO, 1000 ppm NH₃, 8% O₂, 5% H₂O, GHSV = 50000 h^-1	[73]

Fig. 3. Reaction mechanism of the NH3-SCR reaction over ZCuOH species. (a) Reprinted with permission from Ref. [72]. Copyright 2021, American Chemical Society. (b) Reprinted with permission from Ref. [29]. Copyright 2023, American Chemical Society.

Table 2 The range of activity prepared by different methods (SSZ-13).

Catalyst	Active range	Preparation method	Conditions	Ref.
Cu-SSZ-13	170-450 °C (T₉₀)	one-pot method	1000 ppm NO, 1000 ppm NH₃, and 10% O₂,	[110]
Cu-SSZ-13	245-460 °C (T₉₀)	one-pot method	500 ppm NO, 530 ppm NH₃, 7% O₂, 5% H₂O, GHSV = 450000 h^-1	[111]
Cu-SSZ-13	250-550 °C (T₉₀)	one-pot method	500 ppm NO, 500 ppm NH₃, 5% O₂, GHSV = 800000 h^-1	[112]
Cu&Zn-SSZ-13	200-600 °C (T₉₀)	one-pot method	600 ppm NO, 600 ppm NH₃, 6% O₂, 5 % H₂O, GHSV ≈ 400000 h^-1	[113]
Cu, M/SSZ-13	250-500 °C (T₉₅)	ion exchange method	350 ppm NO, 350 ppm NH₃, 14% O₂, 2.5% H₂O, GHSV = 100000 h^-1	[116]
Cu-Na-SSZ-13	150-650 °C (T₈₅)	ion exchange method	500 ppm NO, 500 ppm NH₃, 10% O₂, 5% H₂O, GHSV = 80000 h^-1	[104]

Fig. 6. The location of Cu and its migration in different atmospheres. (a) Relative binding energy of Cu2+-2Z under different possible Al arrangements. Reprinted with permission from Ref. [133]. Copyright 2021, Elsevier B.V. (b) HSE06-optimized structures of Cu sites. Reprinted with permission from Ref. [130]. Copyright 2016, American Chemical Society. (c) Cu positions (gray balls) visited during 90 ps of NVT AIMD at 298 K. Reprinted with permission from Ref. [130]. Copyright 2016, American Chemical Society. (d) Cu positions (gray balls) sampled inside the zeolite cage during 90 ps of equilibrated NVT AIMD at 473 K for the most stable NH3-solvated CuI and CuII species. Reprinted with permission from Ref. [130]. Copyright 2016, American Chemical Society. (e) Reactant state (1) [CuI(NH3)2 in the same cage as Al], transition state (2) [CuI(NH3)2 diffusion through 8-MR], and product state (3) [CuI(NH3)2 in the neighboring cage without Al]. Reprinted with permission from Ref. [135]. Copyright 2017, The American Association for the Advancement of Science.

Fig. 7. Proposed low-temperature SCR catalytic cycle. (a) Reprinted with permission from Ref. [142]. Copyright 2017, American Chemical Society. (b) Reprinted with permission from Ref. [135]. Copyright 2017, The American Association for the Advancement of Science.

Fig. 9. (a) (I) Phase-uncorrected k2-weighted FT-EXAFS curves during exposure of the Cu-CHA catalyst to NO/NH3/He (dark blue thick line), followed by 10% O2 in He (gray thin lines; red thick line: final spectrum; dark gray dashed line: pretreatment in O2 by heating in O2 up to 400 °C and subsequently cooling in O2 down to 200 °C prior to XAS data collection, step 1. (II) Illustration of [Cu(NH3)2]+ and (III) μ-η2, η2-peroxo diamino dicopper (side-on) complexes. Atom color code: Cu, green; H, white; O, red; N, blue. Reprinted with permission from Ref. [155]. Copyright 2020, American Chemical Society. (b) Simulation of O2 adsorption and oxidation of two CuI(NH3)2 equivalents. Reprinted with permission from Ref. [135]. Copyright 2017, The American Association for the Advancement of Science.

Fig. 10. Ex-situ Cu speciation phase diagrams based on HSE06-Tsvdw calculations on 1Al (a) and 2Al (b) Cu exchange sites. Regions indicate site composition that minimizes free energy at 2% H2O and given T and PO2. Reprinted with permission from Ref. [130]. Copyright 2016, American Chemical Society.

Fig. 11. (a) Schematic illustration of dynamic 15NH3 exchange between NH4+ and [Cu(NH3)2]+ species in Cu-CHA. Framework Si and Al atoms are depicted in blue and red, respectively, while Cu cations are shown in gold, with orange arrows indicating possible exchange pathways within the Cu-CHA pores. (b) Solid-state 2D exchange 15N NMR spectrum of fresh Cu-CHA recorded at 53 °C following 15NH3 exposure at 120 °C and subsequent reduction in 15NO at 300 °C; 1D projections are displayed along the horizontal and vertical axes. (c) Evolution of on-diagonal (red and blue) and off-diagonal (orange) peak intensities as a function of mixing time in 2D 15N exchange NMR spectra acquired at 53 °C, 11.7 T, and 12.5 kHz MAS for fresh Cu-CHA. (d) Eyring plots of temperature-dependent exchange rate coefficients derived from global fitting of data such as those in panel (c), measured at 41, 53, and 66 °C for fresh (black), 4-h-aged (red), and 16-h-aged (blue) Cu-CHA catalysts; error bars represent uncertainties estimated via Monte Carlo error propagation. Reprinted with permission from Ref. [171]. Copyright 2025, American Chemical Society.

Fig. 13. Schematic diagram of the preparation of a core-shell catalyst. (a) Cu-Ce-La/SSZ-13@ZSM-5 core-shell catalyst. Reprinted with permission from Ref. [195]. Copyright 2020, Elsevier B.V. (b) Cu-SSZ-13@CZO core-shell catalyst. Reprinted with permission from Ref. [196]. Copyright 2022, American Chemical Society.

Table 3 The activity range after hydrothermal aging (SSZ-39).

Catalyst	Active range	Conditions	Ref.
Cu-SSZ-39	250-550 °C (T₈₀)	800 °C, 12 h	[243]
MnCu-SSZ-39	250-550 °C (T₉₀)	850 °C, 12 h	[279]
Cu-SSZ-39	225-450 °C (T₉₀)	900 °C, 5 h	[280]
Cu/Y-SSZ-39	200-550 °C (T₇₀)	900 °C, 10 h	[250]
Cu-SSZ-39	225-500 °C (T₈₅)	850 °C, 16 h	[244]
Cu-Y-SSZ-39	200-550 °C (T₈₀)	940 °C, 3 h	[245]

Fig. 17. The supposed reaction mechanism of NH3-SCR on Cu/SSZ-39. (a) Reprinted with permission from Ref. [248]. Copyright 2021, Elsevier B.V. (b) Reprinted with permission from Ref. [249]. Copyright 2021, American Chemical Society.

Fig. 18. Structure of the fresh, dehydrated Cu-LTA-16-0.48 catalyst. A Cu2+ cation located at the center of a single 6-ring is shown at the right. Reprinted with permission from Ref. [33]. Copyright 2017, Wiley-VCH.

Fig. 20. (a) HRTEM image of as-made ChRbLi-PST-9. (b) ADF-STEM image of ChRbLi-PST-9 obtained along the b-axis after sectioning the nanosheet by ultramicrotome. (c) Projected potential map constructed based on the ADF-STEM image in plane group pmg showing the structure of PST-9 viewed along the b-axis. (d) Simulated powder XRD pattern. (e) Simulated 29Si MAS NMR spectra of as-made ChRbLi-PST-9. (f) 1H NMR spectra of organic SDA, choline. (g,h) Structures of PST-9 along the b-axis and c-axis. Reprinted with permission from Ref. [269]. Copyright 2019, Wiley-VCH.

Fig. 22. (a-d) SCR reaction rates at different temperatures of Cu-T, Cu-ERI, and Cu-OFF before and after hydrothermal aging treatment, and in-situ DRIFTS spectra of NO + O2 saturation adsorption. (e) NH4NO3 decomposition pathway assisted with/without BAS. Reprinted with permission from Ref. [276]. Copyright 2024 American Chemical Society.

Fig. 23. (a) OSDA reported to crystallize CHA and ERI with the candidate OSDA presented. (b) Comparison between the templating energies of the OSDAs with the CHA and ERI frameworks. (c) Relationship between the shape of the OSDAs and their binding energies toward CHA or ERI. Reprinted with permission from Ref. [277]. Copyright 2024, American Chemical Society.

Table 4 Comparison of Cu-zeolite catalysts with different topological structures.

Catalyst	Topological structure	Cu location	Active range (fresh)	Active range (aged)	Primary applications
Cu-ZSM-5	MFI	10-MR, 6-MR	200-450 °C	poor	low-temperature stationary sources
Cu-SSZ-13	CHA	6-MR, 8MR	180-550 °C	225-450 °C (T₉₀, 800 °C, 16 h)	diesel vehicle exhaust
Cu-SSZ-39	AEI	6-MR, 8MR	225-550 °C	225-500 °C (T₈₅, 850 °C, 16 h)	next-generation diesel vehicles
Cu-LTA	LTA	6-MR	250-580 °C	225-500 °C (T₉₀, 900 °C, 24 h)	high-temperature stationary sources
Cu-SSZ-16	AFX	gme, aft	175-600 °C	225-450 °C (T₈₅, 800 °C, 16 h)	gas turbine
Cu-PST-9	PST-9	8-MR	220-500 °C	225-500 °C (T₈₀)	multifunctional catalysis
Cu-OFF/ERI	OFF/ERI	interface 6-MR	175-550 °C	225-500 °C (T₉₀, 750 °C, 16 h)	alternative Cu-SSZ-13

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Fundamental insight into copper-based zeolite catalysts for NH₃-SCR: Two decades’ progress and future perspectives

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