Mechanistic studies of NH3-assisted reduction of mononuclear Cu(ii) cation sites in Cu-CHA zeolites

Wilcox, Laura N.; Krishna, Siddarth H.; Jones, Casey B.; Gounder, Rajamani

doi:10.1039/d1cy01646f

Title: Mechanistic studies of NH₃-assisted reduction of mononuclear Cu(ii) cation sites in Cu-CHA zeolites

Journal Article · Fri Oct 29 00:00:00 EDT 2021 · Catalysis Science and Technology

DOI:https://doi.org/10.1039/d1cy01646f· OSTI ID:1835587

Wilcox, Laura N. ^[1];

^[1]; Jones, Casey B. ^[1];

^[1]

Purdue Univ., West Lafayette, IN (United States)

Cu-Exchanged zeolites catalyze various redox reactions including the selective catalytic reduction (SCR) of NO_x with NH₃ and the partial oxidation of hydrocarbons. The reduction of Cu(II) cations to Cu(I) by NH₃ alone has been observed experimentally, yet fundamental details regarding the Cu active site requirements, reaction stoichiometry, and reaction mechanism remain incompletely understood. Here, we synthesized model Cu-exchanged chabazite (Cu-CHA) zeolites with varying Cu ion densities and distributions of mononuclear Cu(II) ion site types (Cu²⁺, (CuOH)⁺) and studied NH₃-assisted Cu(II) reduction reactions using a combination of spectroscopic, titrimetric, and gas-phase product analysis methods. In situ UV-visible and X-ray absorption spectroscopies were used to monitor and quantify the transient reduction of Cu(II) to Cu(I) during exposure to NH₃ (473 K), in concert with titration methods that use NO and NH₃ co-reductants to fully reduce to the Cu(I) state any residual Cu(II) ions that remained after treatments in NH₃ alone for a given time period. The techniques provide quantitative evidence that both mononuclear Cu(II) site types are able to reduce in NH₃ alone, and do so to similar extents as a function of time. NH₃ temperature programmed reduction (TPR) revealed that the reaction stoichiometry of NH₃-assisted reduction forms approximately one equivalent of N₂ per 6 Cu sites, regardless of Cu speciation or density, consistent with a six-electron reduction process whereby two NH₃ molecules react with six Cu(II) species to produce one N₂ molecule and six Cu(I) species. Furthermore, these findings provide new insights into the reaction pathways and mechanisms by which NH₃ alone reduces mononuclear Cu(II) sites in zeolites, which are undesired side-reactions that occur during steady-state NO_x SCR and can unintentionally influence SCR-relevant spectroscopic or titrimetric characterization experiments.

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Research Organization:: Purdue Univ., West Lafayette, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019026; AC02-06CH11357

OSTI ID:: 1835587

Alternate ID(s):: OSTI ID: 1829329

Journal Information:: Catalysis Science and Technology, Vol. 11, Issue 24; ISSN 2044-4753

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

Progress on Selective Catalytic Ammonia Oxidation (NH ₃ ‐SCO) over Cu−Containing Zeolite‐Based Catalysts Jabłońska, Magdalena ChemCatChem, Vol. 12, Issue 18 https://doi.org/10.1002/cctc.202000649	journal	June 2020
Identification of the active Cu site in standard selective catalytic reduction with ammonia on Cu-SSZ-13 Bates, Shane A.; Verma, Anuj A.; Paolucci, Christopher Journal of Catalysis, Vol. 312 https://doi.org/10.1016/j.jcat.2014.01.004	journal	April 2014
Bis(μ-oxo) versus mono(μ-oxo)dicopper cores in a zeolite for converting methane to methanol: an in situ XAS and DFT investigation Alayon, Evalyn Mae C.; Nachtegaal, Maarten; Bodi, Andras Physical Chemistry Chemical Physics, Vol. 17, Issue 12 https://doi.org/10.1039/C4CP03226H	journal	January 2015
Revisiting the nature of Cu sites in the activated Cu-SSZ-13 catalyst for SCR reaction Borfecchia, E.; Lomachenko, K. A.; Giordanino, F. Chemical Science, Vol. 6, Issue 1 https://doi.org/10.1039/C4SC02907K	journal	January 2015
Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature Narsimhan, Karthik; Iyoki, Kenta; Dinh, Kimberly ACS Central Science, Vol. 2, Issue 6 https://doi.org/10.1021/acscentsci.6b00139	journal	April 2016
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
The Cu-CHA deNO _x Catalyst in Action: Temperature-Dependent NH ₃ -Assisted Selective Catalytic Reduction Monitored by Operando XAS and XES Lomachenko, Kirill A.; Borfecchia, Elisa; Negri, Chiara Journal of the American Chemical Society, Vol. 138, Issue 37 https://doi.org/10.1021/jacs.6b06809	journal	September 2016
Catalytic conversion of methane to methanol over Cu–mordenite Alayon, Evalyn Mae; Nachtegaal, Maarten; Ranocchiari, Marco Chem. Commun., Vol. 48, Issue 3 https://doi.org/10.1039/C1CC15840F	journal	January 2012
Selective catalytic reduction of NO over Cu-AFX zeolites: mechanistic insights from in situ / operando spectroscopic and DFT studies Liu, Chong; Kubota, Hiroe; Amada, Takehiro Catalysis Science & Technology, Vol. 11, Issue 13 https://doi.org/10.1039/D1CY00282A	journal	January 2021
A [Cu ₂ O] ²⁺ core in Cu-ZSM-5, the active site in the oxidation of methane to methanol Woertink, Julia S.; Smeets, Pieter J.; Groothaert, Marijke H. Proceedings of the National Academy of Sciences, Vol. 106, Issue 45 https://doi.org/10.1073/pnas.0910461106	journal	October 2009
Viewpoint on the Partial Oxidation of Methane to Methanol Using Cu- and Fe-Exchanged Zeolites Dinh, Kimberly T.; Sullivan, Mark M.; Serna, Pedro ACS Catalysis, Vol. 8, Issue 9 https://doi.org/10.1021/acscatal.8b01180	journal	August 2018
Oxidation of Ammonia with Molecular Complexes Dunn, Peter L.; Cook, Brian J.; Johnson, Samantha I. Journal of the American Chemical Society, Vol. 142, Issue 42 https://doi.org/10.1021/jacs.0c08269	journal	September 2020
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
Low absorption vitreous carbon reactors for operandoXAS: a case study on Cu/Zeolites for selective catalytic reduction of NO _x by NH ₃ Kispersky, Vincent F.; Kropf, A. Jeremy; Ribeiro, Fabio H. Phys. Chem. Chem. Phys., Vol. 14, Issue 7 https://doi.org/10.1039/C1CP22992C	journal	January 2012
Spectroscopic and chemical characterization of active and inactive Cu species in NO decomposition catalysts based on Cu-ZSM5 Da Costa, Patrick; Modén, Björn; Meitzner, George D. Phys. Chem. Chem. Phys., Vol. 4, Issue 18 https://doi.org/10.1039/B203700A	journal	January 2002
Dioxygen Activation Kinetics over Distinct Cu Site Types in Cu-Chabazite Zeolites Bregante, Daniel T.; Wilcox, Laura N.; Liu, Changming ACS Catalysis, Vol. 11, Issue 19 https://doi.org/10.1021/acscatal.1c03471	journal	September 2021
Formation of [Cu ₂ O ₂ ] ²⁺ and [Cu ₂ O] ²⁺ toward C–H Bond Activation in Cu-SSZ-13 and Cu-SSZ-39 Ipek, Bahar; Wulfers, Matthew J.; Kim, Hacksung ACS Catalysis, Vol. 7, Issue 7 https://doi.org/10.1021/acscatal.6b03005	journal	May 2017
Control of the Cu ion species in Cu-SSZ-13 via the introduction of Co ²⁺ co-cations to improve the NH ₃ -SCR activity Lee, Hwangho; Song, Inhak; Jeon, Se Won Catalysis Science & Technology, Vol. 11, Issue 14 https://doi.org/10.1039/D1CY00623A	journal	January 2021
Time-resolved copper speciation during selective catalytic reduction of NO on Cu-SSZ-13 Marberger, Adrian; Petrov, Andrey W.; Steiger, Patrick Nature Catalysis, Vol. 1, Issue 3 https://doi.org/10.1038/s41929-018-0032-6	journal	March 2018
Insights into the Speciation of Cu in the Cu-H-Mordenite Catalyst for the Oxidation of Methane to Methanol Brezicki, Gordon; Kammert, James D.; Gunnoe, T. Brent ACS Catalysis, Vol. 9, Issue 6 https://doi.org/10.1021/acscatal.9b00852	journal	April 2019
Identification of Kinetic and Spectroscopic Signatures of Copper Sites for Direct Oxidation of Methane to Methanol Sushkevich, Vitaly L.; Artsiusheuski, Mikalai; Klose, Daniel Angewandte Chemie International Edition, Vol. 60, Issue 29 https://doi.org/10.1002/anie.202101628	journal	June 2021
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
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
Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13 Paolucci, Christopher; Verma, Anuj A.; Bates, Shane A. Angewandte Chemie International Edition, Vol. 53, Issue 44 https://doi.org/10.1002/anie.201407030	journal	September 2014
Speciation of Cu Cations in Cu-CHA Catalysts for NH ₃ -SCR: Effects of SiO ₂ /AlO ₃ Ratio and Cu-Loading Investigated by Transient Response Methods Villamaina, R.; Liu, Shaojun; Nova, I. ACS Catalysis, Vol. 9, Issue 10 https://doi.org/10.1021/acscatal.9b02578	journal	August 2019
The H2O Effect on Cu Speciation in Cu-CHA-Catalysts for NH3-SCR Probed by NH3 Titration Villamaina, Roberta; Gramigni, Federica; Iacobone, Umberto Catalysts, Vol. 11, Issue 7 https://doi.org/10.3390/catal11070759	journal	June 2021
Continuous Partial Oxidation of Methane to Methanol Catalyzed by Diffusion-Paired Copper Dimers in Copper-Exchanged Zeolites Dinh, Kimberly T.; Sullivan, Mark M.; Narsimhan, Karthik Journal of the American Chemical Society, Vol. 141, Issue 29 https://doi.org/10.1021/jacs.9b04906	journal	June 2019
Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol Grundner, Sebastian; Markovits, Monica A. C.; Li, Guanna Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8546	journal	June 2015
Characterization of Cu-exchanged SSZ-13: a comparative FTIR, UV-Vis, and EPR study with Cu-ZSM-5 and Cu-β with similar Si/Al and Cu/Al ratios Giordanino, Filippo; Vennestrøm, Peter N. R.; Lundegaard, Lars F. Dalton Transactions, Vol. 42, Issue 35 https://doi.org/10.1039/c3dt50732g	journal	January 2013
Cu-ZSM-5 Zeolites for the Formation of Methanol from Methane and Oxygen: Probing the Active Sites and Spectator Species Beznis, Nadzeya V.; Weckhuysen, Bert M.; Bitter, Johannes H. Catalysis Letters, Vol. 138, Issue 1-2 https://doi.org/10.1007/s10562-010-0380-6	journal	June 2010
Autoreduction of Copper in Zeolites: Role of Topology, Si/Al Ratio, and Copper Loading Sushkevich, Vitaly L.; Smirnov, Andrei V.; van Bokhoven, Jeroen A. The Journal of Physical Chemistry C, Vol. 123, Issue 15 https://doi.org/10.1021/acs.jpcc.9b00986	journal	March 2019
Quasi- operando quantification of Cu( ii ) ions in Cu-SSZ-13 catalyst by an NH ₃ temperature-programmed reduction method Ma, Yue; Wu, Xiaodong; Ding, Jiancai Chemical Communications, Vol. 57, Issue 15 https://doi.org/10.1039/D0CC07346F	journal	January 2021
Automotive NO _x abatement using zeolite-based technologies Gounder, Rajamani; Moini, Ahmad Reaction Chemistry & Engineering, Vol. 4, Issue 6 https://doi.org/10.1039/C9RE90030F	journal	January 2019
A Consistent Reaction Scheme for the Selective Catalytic Reduction of Nitrogen Oxides with Ammonia Janssens, Ton V. W.; Falsig, Hanne; Lundegaard, Lars F. ACS Catalysis, Vol. 5, Issue 5 https://doi.org/10.1021/cs501673g	journal	March 2015
Methane-to-methanol conversion over zeolite Cu-SSZ-13, and its comparison with the selective catalytic reduction of NO _x with NH ₃ Oord, Ramon; Schmidt, Joel E.; Weckhuysen, Bert M. Catalysis Science & Technology, Vol. 8, Issue 4 https://doi.org/10.1039/C7CY02461D	journal	January 2018
Effects of dioxygen pressure on rates of NOx selective catalytic reduction with NH3 on Cu-CHA zeolites Jones, Casey B.; Khurana, Ishant; Krishna, Siddarth H. Journal of Catalysis, Vol. 389 https://doi.org/10.1016/j.jcat.2020.05.022	journal	September 2020
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
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
Controlling the Isolation and Pairing of Aluminum in Chabazite Zeolites Using Mixtures of Organic and Inorganic Structure-Directing Agents Di Iorio, John R.; Gounder, Rajamani Chemistry of Materials, Vol. 28, Issue 7 https://doi.org/10.1021/acs.chemmater.6b00181	journal	March 2016
On the Redox Mechanism of Low‐Temperature NH ₃ ‐SCR over Cu‐CHA: A Combined Experimental and Theoretical Study of the Reduction Half Cycle Hu, Wenshuo; Selleri, Tommaso; Gramigni, Federica Angewandte Chemie International Edition, Vol. 60, Issue 13 https://doi.org/10.1002/anie.202014926	journal	February 2021
Perspective on SCR NO _x control for diesel vehicles Lambert, Christine K. Reaction Chemistry & Engineering, Vol. 4, Issue 6 https://doi.org/10.1039/C8RE00284C	journal	January 2019
Low‐T CO Oxidation over Cu−CHA Catalysts in Presence of NH ₃ : Probing the Mobility of Cu ^II Ions and the Role of Multinuclear Cu ^II Species Villamaina, Roberta; Iacobone, Umberto; Nova, Isabella ChemCatChem, Vol. 12, Issue 15 https://doi.org/10.1002/cctc.202000734	journal	June 2020
Ammonia-Containing Species Formed in Cu-Chabazite As Per In Situ EPR, Solid-State NMR, and DFT Calculations Moreno-González, Marta; Hueso, Beatriz; Boronat, Mercedes The Journal of Physical Chemistry Letters, Vol. 6, Issue 6 https://doi.org/10.1021/acs.jpclett.5b00069	journal	March 2015

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