Recent advances in bimetallic small-pore zeolite catalysts for ammonia-assisted selective catalytic reduction of NO_x

Abstract

Bimetallic small-pore zeolites containing Cu ions and secondary metal ions present a potential application value for ammonia-assisted selective catalytic reduction of nitrogen oxides (NO_x), showing superior catalytic activity and excellent hydrothermal stability compared to monometallic Cu-zeolites. The idea of introducing secondary metal ions aims to modulate the properties of Cu active sites. This review first summarizes the strategies of incorporating secondary metal ions into zeolites. Then, we delve into the impacts of varying loadings of secondary metal ions on the catalytic performance of zeolites. Finally, we emphasize the synergistic interactions between secondary metal ions and active Cu sites, focusing on their effects on the distribution, stability, and activity of the Cu active sites, which are adjusted by the presence of secondary metal ions. In conclusion, we wrap up this review and provide perspectives on the design and in-depth study on metal ions-doped Cu-zeolite catalysts.

Keywords

Zeolite / small pores / Cu-SSZ-13 / NH₃-SCR reaction / bimetallic ions / Cu active sites

References

[1] Richter A,Nüss H,Niemeier U.Increase in tropospheric nitrogen dioxide over China observed from space.Nature2005;437:129-32

[2] Kim CH,Dahlberg K.Strontium-doped perovskites rival platinum catalysts for treating NO_x in simulated diesel exhaust.Science2010;327:1624-7

[3] Han L,Gao M.Selective catalytic reduction of NO_x with NH₃ by using novel catalysts: state of the art and future prospects.Chem Rev2019;119:10916-76

[4] Shan Y,Zhang Y.Selective catalytic reduction of NO_x with NH₃: opportunities and challenges of Cu-based small-pore zeolites.Natl Sci Rev2021;8:nwab010 PMCID:PMC8566184

[5] Wei Y,Chen M.Coaxial 3D printing of zeolite-based core-shell monolithic Cu-SSZ-13@SiO₂ catalysts for diesel exhaust treatment.Adv Mater2024;36:e2302912

[6] Chen M,Liu C.Enhancing performance of Fe-SSZ-13 and Cu-Fe-SSZ-13 zeolites for selective catalytic reduction reaction via post-treatment method.Mater Lett2023;349:134872

[7] Twigg MV.Progress and future challenges in controlling automotive exhaust gas emissions.Appl Catal B Environ2007;70:2-15

[8] Zhang R,Lei Z.Selective transformation of various nitrogen-containing exhaust gases toward N₂ over zeolite catalysts.Chem Rev2016;116:3658-721

[9] Beale AM,Lezcano-Gonzalez I,Szanyi J.Recent advances in automotive catalysis for NO_x emission control by small-pore microporous materials.Chem Soc Rev2015;44:7371-405

[10] Chen M,Yang G.Enhanced performance for selective catalytic reduction of NO_x with NH₃ over nanosized Cu/SAPO-34 catalysts.ChemCatChem2019;11:3865-70

[11] Djerad S,Crocoll M.Effect of vanadia and tungsten loadings on the physical and chemical characteristics of V₂O₅-WO₃/TiO₂ catalysts.J Mol Catal A Chem2004;208:257-65

[12] Martín JA,Ávila P,Blanco J.Nitrous oxide formation in low temperature selective catalytic reduction of nitrogen oxides with V₂O₅/TiO₂ catalysts.Appl Catal B Environ2007;70:330-4

[13] Topsøe NY.Mechanism of the selective catalytic reduction of nitric oxide by ammonia elucidated by in situ on-line fourier transform infrared spectroscopy.Science1994;265:1217-9

[14] Li J,Ma L,Yang RT.Low-temperature selective catalytic reduction of NO_x with NH₃ over metal oxide and zeolite catalysts - a review.Catal Today2011;175:147-56

[15] Chen J,Bao S.A review on the characterization of metal active sites over Cu-based and Fe-based zeolites for NH₃-SCR.RSC Adv2022;12:27746-65 PMCID:PMC9517171

[16] Wang Y,Liu Z.Selective catalytic reduction of NO_x by NH₃ over Cu-AEI zeolite catalyst: current status and future perspectives.Appl Catal B Environ2024;343:123479

[17] Guo RT,Wei LG,Zhou J.Recent progress of low-temperature selective catalytic reduction of NO_x with NH₃ over manganese oxide-based catalysts.Phys Chem Chem Phys2022;24:6363-82

[18] Gao F,Yi H.Promotional mechanisms of activity and SO₂ tolerance of Co- or Ni-doped MnOx-CeO₂ catalysts for SCR of NOx with NH₃ at low temperature.Chem Eng J2017;317:20-31

[19] Gao F,Yi H,Wang J.Improvement of activity, selectivity and H₂O&SO₂-tolerance of micro-mesoporous CrMn₂O₄ spinel catalyst for low-temperature NH₃-SCR of NOx.Appl Surf Sci2019;466:411-24

[20] Li Y.Emerging applications of zeolites in catalysis, separation and host–guest assembly.Nat Rev Mater2021;6:1156-74

[21] Li Y,Yu J.Applications of zeolites in sustainable chemistry.Chem2017;3:928-49

[22] Kerstens D,Van Waeyenberg J,Yu J.State of the art and perspectives of hierarchical zeolites: practical overview of synthesis methods and use in catalysis.Adv Mater2020;32:e2004690

[23] Sun Q,Yu J.Advances in catalytic applications of zeolite-supported metal catalysts.Adv Mater2021;33:e2104442

[24] Sun Q,Yu J.The state-of-the-art synthetic strategies for SAPO-34 zeolite catalysts in methanol-to-olefin conversion.Natl Sci Rev2018;5:542-58

[25] Liu L.Confining isolated atoms and clusters in crystalline porous materials for catalysis.Nat Rev Mater2021;6:244-63

[26] Iwamoto M,Mine Y,Mikuriya S.Copper(II) ion-exchanged ZSM-5 zeolites as highly active catalysts for direct and continuous decomposition of nitrogen monoxide.J Chem Soc Chem Commun1986;1272-3

[27] Ochońska J,Jodłowski P.Copper exchanged ultrastable zeolite Y - A catalyst for NH₃-SCR of NO_x from stationary biogas engines.Catal Today2012;191:6-11

[28] Sullivan JA,Morris M.Conditions in which Cu-ZSM-5 outperforms supported vanadia catalysts in SCR of NO_x by NH₃.Appl Catal B Environ1995;7:137-51

[29] Sjövall H,Olsson L.Detailed kinetic modeling of NH₃ SCR over Cu-ZSM-5.Appl Catal B Environ2009;92:138-53

[30] Chen H.Activity and durability of Fe/ZSM-5 catalysts for lean burn NO_x reduction in the presence of water vapor.Catal Today1998;42:73-83

[31] Shi X,Xie L,He H.NH₃-SCR performance of fresh and hydrothermally aged Fe-ZSM-5 in standard and fast selective catalytic reduction reactions.Environ Sci Technol2013;47:3293-8

[32] De-La-Torre U,Moliner M,Corma A.Cu-zeolite catalysts for NO_x removal by selective catalytic reduction with NH₃ and coupled to NO storage/reduction monolith in diesel engine exhaust aftertreatment systems.Appl Catal B Environ2016;187:419-27

[33] Xin Y,Zhang Z.Zeolitic materials for DeNO_x selective catalytic reduction.ChemCatChem2018;10:29-41

[34] Andana T,Gao F,Pereira-hernandez X.Recent advances in hybrid metal oxide–zeolite catalysts for low-temperature selective catalytic reduction of NOx by ammonia.Appl Catal B Environ2021;291:120054

[35] Peden CH.Cu/Chabazite catalysts for ‘Lean-Burn’ vehicle emission control.J Catal2019;373:384-9

[36] Lezcano-Gonzaleza I,van der Bijb HE.Chemical deactivation of Cu-SSZ-13 ammonia selective catalytic reduction (NH₃-SCR) systems.Appl Catal B2014;154-5:339-49

[37] Deka U,Weckhuysen BM.Local environment and nature of Cu active sites in zeolite-based catalysts for the selective catalytic reduction of NO_x.ACS Catal2013;3:413-27

[38] Wilken N,Kamasamudram K.Mechanistic investigation of hydrothermal aging of Cu-Beta for ammonia SCR.Appl Catal B Environ2012:111-2:58

[39] Frey AM,Due-Hansen J,Christensen CH.Fe-BEA zeolite catalysts for NH₃-SCR of NO_x.Catal Lett2009;130:1-8

[40] Rahkamaa-tolonen K,Lomma M,Keiski RL.The effect of NO₂ on the activity of fresh and aged zeolite catalysts in the NH₃-SCR reaction.Catal Today2005;100:217-22

[41] Kwak JH,Kim DH,Peden CH.Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NO_x with NH₃.J Catal2010;275:187-90

[42] Kwak JH,Burton SD,Lee JH.Effects of hydrothermal aging on NH₃-SCR reaction over Cu/zeolites.J Catal2012;287:203-9

[43] Wang Y,Chen M.Low-silica Cu-CHA zeolite enriched with Al pairs transcribed from silicoaluminophosphate seed: synthesis and ammonia selective catalytic reduction performance.Angew Chem Int Ed Engl2023;62:e202306174

[44] Ryu T,Seo S.Fully copper-exchanged high-silica LTA zeolites as unrivaled hydrothermally stable NH₃-SCR catalysts.Angew Chem Int Ed Engl2017;56:3256-60

[45] Jo D,Ryu T.Economical synthesis of high-silica LTA zeolites: a step forward in developing a new commercial NH₃-SCR catalyst.Appl Catal B Environ2019;243:212-9

[46] Jo D,Park GT.Synthesis of high-silica LTA and UFI zeolites and NH₃-SCR performance of their copper-exchanged form.ACS Catal2016;6:2443-7

[47] Kim J,Kim DH.Facile synthesis of KFI-type zeolite and its application to selective catalytic reduction of NO_x with NH₃.ACS Catal2017;7:6070-81

[48] Han S,Wang L.Potassium-directed sustainable synthesis of new high silica small-pore zeolite with KFI structure (ZJM-7) as an efficient catalyst for NH₃-SCR reaction.Appl Catal B Environ2021;281:119480

[49] Zhu N,Shan W.Distinct NO₂ effects on Cu-SSZ-13 and Cu-SSZ-39 in the selective catalytic reduction of NO_x with NH₃.Environ Sci Technol2020;54:15499-506

[50] Moliner M,Palomares E,Corma A.Cu-SSZ-39, an active and hydrothermally stable catalyst for the selective catalytic reduction of NOx.Chem Commun2012;48:8264-6

[51] Ming S,Fan C.The effect of copper loading and silicon content on catalytic activity and hydrothermal stability of Cu-SAPO-18 catalyst for NH₃-SCR.Appl Catal A Gen2018;559:47-56

[52] Fickel DW,Lauterbach JA.The ammonia selective catalytic reduction activity of copper-exchanged small-pore zeolites.Appl Catal B Environ2011;102:441-8

[53] Godiksen A,Vennestrøm PNR.Coordination environment of copper sites in Cu-CHA zeolite investigated by electron paramagnetic resonance.J Phys Chem C2014;118:23126-38

[54] Chen D,Lei H.Copper site motion promotes catalytic NO_x reduction under zeolite confinement.Environ Sci Technol2023;57:16121-30

[55] Paolucci C,Parekh AA.Dynamic multinuclear sites formed by mobilized copper ions in NO_x selective catalytic reduction.Science2017;357:898-903

[56] Paolucci C,Khurana I.Catalysis in a cage: condition-dependent speciation and dynamics of exchanged Cu cations in SSZ-13 zeolites.J Am Chem Soc2016;138:6028-48

[57] Kim YJ,Min KM,Nam I.Hydrothermal stability of CuSSZ13 for reducing NOx by NH₃.J Catal2014;311:447-57

[58] Han S,Cheng S,Dai H.Effect of the hydrothermal aging temperature and Cu/Al ratio on the hydrothermal stability of CuSSZ-13 catalysts for NH₃-SCR.Catal Sci Technol2017;7:703-17

[59] Song J,Walter ED.Toward rational design of Cu/SSZ-13 selective catalytic reduction catalysts: implications from atomic-level understanding of hydrothermal stability.ACS Catal2017;7:8214-27

[60] Iorio JR, Gounder R. Controlling the isolation and pairing of aluminum in chabazite zeolites using mixtures of organic and inorganic structure-directing agents.Chem Mater2016;28:2236-47

[61] Iorio JR, Nimlos CT, Gounder R. Introducing catalytic diversity into single-site chabazite zeolites of fixed composition via synthetic control of active site proximity.ACS Catal2017;7:6663-74

[62] Zhang J,Zhang L.Importance of controllable Al sites in CHA framework by crystallization pathways for NH₃-SCR reaction.Appl Catal B Environ2020;277:119193

[63] Gao F,Washton NM,Szanyi J.Effects of alkali and alkaline earth cocations on the activity and hydrothermal stability of Cu/SSZ-13 NH₃-SCR catalysts.ACS Catal2015;5:6780-91

[64] Usui T,Ibe S.Improve the hydrothermal stability of Cu-SSZ-13 zeolite catalyst by loading a small amount of Ce.ACS Catal2018;8:9165-73

[65] Chen M,Xue W.Unveiling secondary-ion-promoted catalytic properties of Cu-SSZ-13 zeolites for selective catalytic reduction of NO_x.J Am Chem Soc2022;144:12816-24

[66] Chen M,Wei Y.La ions-enhanced NH₃-SCR performance over Cu-SSZ-13 catalysts.Nano Res2023;16:12126-33

[67] Kang N,Wen Chen Z.Understanding enhancement of strong Copper-Yttrium interactions on catalytic properties of Cu/Y-SSZ-13 for NH₃-SCR.Chem Eng J2023;475:146114

[68] Iwasaki M.A comparative study of “standard”, “fast” and “NO₂” SCR reactions over Fe/zeolite catalyst.Appl Catal A Gen2010;390:71-7

[69] Colombo M,Tronconi E.A comparative study of the NH₃-SCR reactions over a Cu-zeolite and a Fe-zeolite catalyst.Catal Today2010;151:223-30

[70] Colombo M,Tronconi E.Detailed kinetic modeling of the NH₃–NO/NO₂ SCR reactions over a commercial Cu-zeolite catalyst for Diesel exhausts after treatment.Catal Today2012;197:243-55

[71] Bendrich M,Hayes R.Unified mechanistic model for Standard SCR, Fast SCR, and NO₂ SCR over a copper chabazite catalyst.Appl Catal B Environ2018;222:76-87

[72] Grossale A,Tronconi E,Weibel M.The chemistry of the NO/NO₂–NH₃ “fast” SCR reaction over Fe-ZSM5 investigated by transient reaction analysis.J Catal2008;256:312-22

[73] Janssens TVW,Lundegaard LF.A consistent reaction scheme for the selective catalytic reduction of nitrogen oxides with ammonia.ACS Catal2015;5:2832-45

[74] Schuler A,Kiwic P.NH₃-SCR on Fe zeolite catalysts - from model setup to NH₃ dosing.Chem Eng J2009;154:333-40

[75] Chen H,Kollar M.A comparative study of N₂O formation during the selective catalytic reduction of NOx with NH₃ on zeolite supported Cu catalysts.J Catal2015;329:490-8

[76] Shi X,Shan W.Hydrothermal deactivation of Fe-ZSM-5 prepared by different methods for the selective catalytic reduction of NO_x with NH₃.Chin J Catal2012;33:454-64

[77] Yin C,Li X.Selective catalytic reduction of nitric oxide with ammonia over high-activity Fe/SSZ-13 and Fe/one-pot-synthesized Cu-SSZ-13 catalysts.Catal Sci Technol2016;6:7561-8

[78] Wang Y,Liu F.Effect of preparation methods on the performance of CuFe-SSZ-13 catalysts for selective catalytic reduction of NO_x with NH₃.J Environ Sci2019;81:195-204

[79] Wan J,Zhao R.One-pot synthesis of Fe/Cu-SSZ-13 catalyst and its highly efficient performance for the selective catalytic reduction of nitrogen oxide with ammonia.J Environ Sci2021;100:306-16

[80] Jouini H,Petitto C.Characterization and NH₃-SCR reactivity of Cu-Fe-ZSM-5 catalysts prepared by solid state ion exchange: the metal exchange order effect.Micropor Mesopor Mat2018;260:217-26

[81] Sultana A,Suzuki K.Tuning the NOx conversion of Cu-Fe/ZSM-5 catalyst in NH₃-SCR.Catal Commun2013;41:21-5

[82] Ren L,Yang C.Designed copper-amine complex as an efficient template for one-pot synthesis of Cu-SSZ-13 zeolite with excellent activity for selective catalytic reduction of NOx by NH₃.Chem Commun2011;47:9789-91

[83] Xie L,Shi X,He H.Effects of post-treatment method and Na co-cation on the hydrothermal stability of Cu-SSZ-13 catalyst for the selective catalytic reduction of NO with NH₃.Appl Catal B Environ2015;179:206-12

[84] Xie L,Ren L,Xiao FS.Excellent performance of one-pot synthesized Cu-SSZ-13 catalyst for the selective catalytic reduction of NOx with NH₃.Environ Sci Technol2014;48:566-72

[85] Shan Y,Yu Y,Shi X.Precise control of post-treatment significantly increases hydrothermal stability of in-situ synthesized cu-zeolites for NH₃-SCR reaction.Appl Catal B Environ2020;266:118655

[86] Zhang T,Liu J.High activity and wide temperature window of Fe-Cu-SSZ-13 in the selective catalytic reduction of NO with ammonia.AIChE J2015;61:3825-37

[87] Xu R,Liu N,Zhang J.Understanding Zn Functions on hydrothermal stability in a one-pot-synthesized Cu&Zn-SSZ-13 catalyst for NH₃ selective catalytic reduction.ACS Catal2020;10:6197-212

[88] Zhou X,Guo Z.One-pot hydrothermal synthesis of dual metal incorporated CuCe-SAPO-34 zeolite for enhancing ammonia selective catalytic reduction.J Hazard Mater2021;405:124177

[89] Du J,Shi X,Zhang Y.Promoting effect of Mn on in situ synthesized Cu-SSZ-13 for NH₃-SCR.Catalysts2020;10:1375

[90] Chen Z,Guo L.The promoting mechanism of in situ Zr doping on the hydrothermal stability of Fe-SSZ-13 catalyst for NH₃-SCR reaction.Appl Catal B Environ2021;286:119816

[91] Pang L,Shao L.The Ce doping Cu/ZSM-5 as a new superior catalyst to remove NO from diesel engine exhaust.Chem Eng J2014;253:394-401

[92] Wang J,Tang X,Jin T.The promotion effect of niobium on the low-temperature activity of Al-rich Cu-SSZ-13 for selective catalytic reduction of NO_x with NH₃.Chem Eng J2021;418:129433

[93] Zhu N,Li S.Understanding Na functions on distribution of Cu species within Cu-SSZ-13 for the selective reduction of NO_x with NH₃.Sep Purif Technol2024;347:127630

[94] Lv W,Wang P.Regulation of Al distributions and Cu²⁺ locations in SSZ-13 zeolites for NH₃-SCR of NO by different alkali metal cations.J Catal2021;393:190-201

[95] Lee H,Jeon SW.Control of the Cu ion species in Cu-SSZ-13 via the introduction of Co²⁺ co-cations to improve the NH₃-SCR activity.Catal Sci Technol2021;11:4838-48

[96] U.S. Drive. Advanced combustion and emission control technical team roadmap. 2013. Available from: https://www1.eere.energy.gov/vehiclesandfuels/pdfs/program/acec_roadmap_june2013.pdf. [Last accessed on 5 Aug 2024]

[97] Zhang T,Li J.Design and synthesis of core-shell structured meso-Cu-SSZ-13@mesoporous aluminosilicate catalyst for SCR of NO_x with NH₃: enhancement of activity, hydrothermal stability and propene poisoning resistance.Appl Catal B Environ2016;195:48-58

[98] Shih AJ,Khurana I.Influence of ZCuOH, Z₂Cu, and extraframework Cu_xO_y species in Cu-SSZ-13 on N₂O formation during the selective catalytic reduction of NO_x with NH₃.ACS Catal2021;11:10362-76

[99] Zhang Y,Zhang T.Revealing the synergistic deactivation mechanism of hydrothermal aging and SO₂ poisoning on Cu/SSZ-13 under SCR condition.Environ Sci Technol2022;56:1917-26

[100] Ye X,Wang RP.Deactivation of Cu-exchanged automotive-emission NH₃-SCR catalysts elucidated with nanoscale resolution using scanning transmission X-ray microscopy.Angew Chem Int Ed Engl2020;59:15610-7 PMCID:PMC7522683

[101] Cui Y,Mei D.Revisiting effects of alkali metal and alkaline earth co-cation additives to Cu/SSZ-13 selective catalytic reduction catalysts.J Catal2019;378:363-75

[102] Chen M,Wei Y.Improving the hydrothermal stability of Al-rich Cu-SSZ-13 zeolite via Pr-ion modification.Chem Sci2024;15:5548-54 PMCID:PMC11023032

[103] Clark AH,Steiger P.Selective catalytic reduction of NO with NH₃ on Cu-SSZ-13: deciphering the low and high-temperature rate-limiting steps by transient XAS experiments.ChemCatChem2020;12:1429-35

[104] Chen L,Vennestrøm PNR,Skoglundh M.A complete multisite reaction mechanism for low-temperature NH₃-SCR over Cu-CHA.ACS Catal2020;10:5646-56

[105] Liu C,Toyao T,Shimizu K.Mechanistic insights into the oxidation of copper(I) species during NH₃-SCR over Cu-CHA zeolites: a DFT study.Catal Sci Technol2020;10:3586-93

[106] Feng Y,Janssens TVW.First-principles microkinetic model for low-temperature NH₃-assisted selective catalytic reduction of NO over Cu-CHA.ACS Catal2021;11:14395-407

[107] Hu W,Gramigni F.On the redox mechanism of low-temperature NH₃-SCR over Cu-CHA: a combined experimental and theoretical study of the reduction half cycle.Angew Chem Int Ed Engl2021;60:7197-204

[108] Feng Y,Vennestrøm PNR,Skoglundh M.The role of H⁺- and Cu⁺-sites for N₂O formation during NH₃-SCR over Cu-CHA.J Phys Chem C2021;125:4595-601

[109] Chen Z,Qu H,Xie H.Controllable positions of Cu²⁺ to enhance low-temperature SCR activity on novel Cu-Ce-La-SSZ-13 by a simple one-pot method.Chem Commun2020;56:2360-3

[110] Yue Y,Qin P.One-pot synthesis of FeCu-SSZ-13 zeolite with superior performance in selective catalytic reduction of NO by NH₃ from natural aluminosilicates.Chem Eng J2020;398:125515

[111] Chen M,Han J,Yu J.Enhancing catalytic performance of Cu-SSZ-13 for the NH₃-SCR reaction via in situ introduction of Fe³⁺ with diatomite.Mater Chem Front2021;5:7787-95

[112] Han J,Song C.Rapid synthesis and NH₃-SCR activity of SSZ-13 zeolite via coal gangue.Green Chem2020;22:219-29