Quantitative Cu Counting Methodologies for Cu/SSZ-13 Selective Catalytic Reduction Catalysts by Electron Paramagnetic Resonance Spectroscopy

Zhang, Yani; Wu, Yiqing; Peng, Yue; Li, Junhua; Walter, Eric D.; Chen, Ying; Washton, Nancy M.; Szanyi, Janos; Wang, Yong; Gao, Feng

doi:10.1021/acs.jpcc.0c07971

Title: Quantitative Cu Counting Methodologies for Cu/SSZ-13 Selective Catalytic Reduction Catalysts by Electron Paramagnetic Resonance Spectroscopy

Journal Article · Thu Dec 10 00:00:00 EST 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c07971· OSTI ID:1756439

Zhang, Yani ^[1]; Wu, Yiqing ^[2];

^[3];

^[2];

^[4];

^[2]

Tsinghua Univ., Beijing (China); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Tsinghua Univ., Beijing (China)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)

Here, two Cu/SSZ-13 selective catalytic reduction (SCR) catalysts with distinct Si/Al ratios and isolated Z2Cu and ZCuOH distributions are prepared for in situ electron paramagnetic resonance (EPR) spectroscopic studies. These in situ studies include dehydration, titration of dehydrated samples with NO+O₂ and NH₃, titration of NH₃ saturated samples with NO+O₂, and finally steady-state standard NH₃-SCR reaction. During dehydration, EPR active hydrated ZCuOH loses H₂O ligands and becomes EPR silent due to a pseudo Jahn-Teller effect; a portion of ZCuOH also undergoes autoreduction to ZCu(I) species, a process that also induces EPR invisibility. During NO+O₂ treatment of dehydrated samples, ZCu(I) species are oxidized to Cu(II)-NO₃^- species, regaining EPR visibility. During NH3 titration, EPR silent dehydrated ZCuOH can also regain EPR visibility by coordinating with NH₃ ligands. During NO+O₂ titration of NH₃-saturated samples, EPR active Cu contents first decrease due to Cu(II) reduction to Cu(I), and then increase due to Cu(II)-NO₃^- species formation. However, the Cu(II)-NO₃^- formation chemistry is substantially slower for the Si/Al = 36 catalyst. In steady-state SCR studies, the EPR active content decreases with increasing temperature in the kinetically controlled low-temperature regime and becomes largely invariant in mass-transfer limited regime. Importantly, Cu sites in the SCR more active Si/Al = 6 catalyst display substantially higher EPR visibility than the SCR less active Si/Al = 36 catalyst at any reaction temperatures tested. The higher Cu loading for the former catalyst is believed to be key for this difference.

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

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; National Natural Science Foundation of China (NSFC)

Grant/Contract Number:: AC05-76RL01830; 21936005

OSTI ID:: 1756439

Report Number(s):: PNNL-SA-156011

Journal Information:: Journal of Physical Chemistry. C, Vol. 124, Issue 51; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

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
Integrated operando X-ray absorption and DFT characterization of Cu–SSZ-13 exchange sites during the selective catalytic reduction of NOx with NH3 McEwen, J. -S.; Anggara, T.; Schneider, W. F. Catalysis Today, Vol. 184, Issue 1 https://doi.org/10.1016/j.cattod.2011.11.037	journal	April 2012
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
Introducing Catalytic Diversity into Single-Site Chabazite Zeolites of Fixed Composition via Synthetic Control of Active Site Proximity Di Iorio, John R.; Nimlos, Claire T.; Gounder, Rajamani ACS Catalysis, Vol. 7, Issue 10 https://doi.org/10.1021/acscatal.7b01273	journal	September 2017
Identification and Quantification of Copper Sites in Zeolites by Electron Paramagnetic Resonance Spectroscopy Godiksen, Anita; Vennestrøm, Peter N. R.; Rasmussen, Søren B. Topics in Catalysis, Vol. 60, Issue 1-2 https://doi.org/10.1007/s11244-016-0731-7	journal	September 2016
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
Nature and Topology of Metal–Oxygen Binding Sites in Zeolite Materials: ¹⁷ O High‐Resolution EPR Spectroscopy of Metal‐Loaded ZSM‐5 Morra, Elena; Signorile, Matteo; Salvadori, Enrico Angewandte Chemie International Edition, Vol. 58, Issue 36 https://doi.org/10.1002/anie.201906488	journal	September 2019
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
Using Transient FTIR Spectroscopy to Probe Active Sites and Reaction Intermediates for Selective Catalytic Reduction of NO on Cu/SSZ-13 Catalysts Zhang, Yani; Peng, Yue; Li, Kezhi ACS Catalysis, Vol. 9, Issue 7 https://doi.org/10.1021/acscatal.9b00759	journal	May 2019
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
Copper Coordination in Cu-SSZ-13 and Cu-SSZ-16 Investigated by Variable-Temperature XRD Fickel, Dustin W.; Lobo, Raul F. The Journal of Physical Chemistry C, Vol. 114, Issue 3 https://doi.org/10.1021/jp9105025	journal	December 2009
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
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
Structural implications derived from the analysis of electron paramagnetic resonance spectra of natural and artificial copper proteins Peisach, J.; Blumberg, W. E. Archives of Biochemistry and Biophysics, Vol. 165, Issue 2 https://doi.org/10.1016/0003-9861(74)90298-7	journal	December 1974
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
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
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
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
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
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
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
The impact of automotive catalysis on the United Nations sustainable development goals Wang, Aiyong; Olsson, Louise Nature Catalysis, Vol. 2, Issue 7 https://doi.org/10.1038/s41929-019-0318-3	journal	July 2019
Investigating the Low Temperature Formation of Cu II ‐(N,O) Species on Cu‐CHA Zeolites for the Selective Catalytic Reduction of NO x Negri, Chiara; Hammershøi, Peter S.; Janssens, Ton V. W. Chemistry – A European Journal, Vol. 24, Issue 46 https://doi.org/10.1002/chem.201802769	journal	June 2018
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
Unraveling the mysterious failure of Cu/SAPO-34 selective catalytic reduction catalysts Wang, Aiyong; Chen, Ying; Walter, Eric D. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09021-3	journal	March 2019
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
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
Current Understanding of Cu-Exchanged Chabazite Molecular Sieves for Use as Commercial Diesel Engine DeNOx Catalysts Gao, Feng; Kwak, Ja Hun; Szanyi, Janos Topics in Catalysis, Vol. 56, Issue 15-17 https://doi.org/10.1007/s11244-013-0145-8	journal	August 2013
Composition-driven Cu-speciation and reducibility in Cu-CHA zeolite catalysts: a multivariate XAS/FTIR approach to complexity Martini, A.; Borfecchia, E.; Lomachenko, K. A. Chemical Science, Vol. 8, Issue 10 https://doi.org/10.1039/C7SC02266B	journal	January 2017
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
Current state of the art and future needs for automotive exhaust catalysis Lambert, Christine K. Nature Catalysis, Vol. 2, Issue 7 https://doi.org/10.1038/s41929-019-0303-x	journal	July 2019
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
Cu-CHA – a model system for applied selective redox catalysis Borfecchia, Elisa; Beato, Pablo; Svelle, Stian Chemical Society Reviews, Vol. 47, Issue 22 https://doi.org/10.1039/C8CS00373D	journal	January 2018
EPR Study of Copper-Exchanged Zeolites: Effects of Correlated g - and A -Strain, Si/Al Ratio, and Parent Zeolite Carl, Patrick J.; Larsen, Sarah C. The Journal of Physical Chemistry B, Vol. 104, Issue 28 https://doi.org/10.1021/jp000015j	journal	July 2000
NO Chemisorption on Cu/SSZ-13: A Comparative Study from Infrared Spectroscopy and DFT Calculations Zhang, Renqin; McEwen, Jean-Sabin; Kollár, Márton ACS Catalysis, Vol. 4, Issue 11 https://doi.org/10.1021/cs500563s	journal	October 2014
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
Overview of the practically important behaviors of zeolite-based urea-SCR catalysts, using compact experimental protocol Kamasamudram, Krishna; Currier, Neal W.; Chen, Xu Catalysis Today, Vol. 151, Issue 3-4 https://doi.org/10.1016/j.cattod.2010.03.055	journal	June 2010
Isolated Cu ²⁺ ions: active sites for selective catalytic reduction of NO Korhonen, Satu T.; Fickel, Dustin W.; Lobo, Raul F. Chem. Commun., Vol. 47, Issue 2 https://doi.org/10.1039/C0CC04218H	journal	January 2011
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
Reaction Pathways and Kinetics for Selective Catalytic Reduction (SCR) of Acidic NO _x Emissions from Power Plants with NH ₃ Zhu, Minghui; Lai, Jun-Kun; Tumuluri, Uma ACS Catalysis, Vol. 7, Issue 12 https://doi.org/10.1021/acscatal.7b03149	journal	November 2017
Dynamic CuII/CuI speciation in Cu-CHA catalysts by in situ Diffuse Reflectance UV–vis-NIR spectroscopy Negri, Chiara; Signorile, Matteo; Porcaro, Natale G. Applied Catalysis A: General, Vol. 578 https://doi.org/10.1016/j.apcata.2019.03.018	journal	May 2019
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
Evidence of Mixed‐Ligand Complexes in Cu−CHA by Reaction of Cu Nitrates with NO/NH ₃ at Low Temperature Negri, Chiara; Borfecchia, Elisa; Cutini, Michele ChemCatChem, Vol. 11, Issue 16 https://doi.org/10.1002/cctc.201900590	journal	June 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
In situ electron paramagnetic resonance: a unique tool for analyzing structure–reactivity relationships in heterogeneous catalysis Brückner, Angelika Chemical Society Reviews, Vol. 39, Issue 12 https://doi.org/10.1039/b919541f	journal	January 2010
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

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
copper catalyst
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In situ EPR
active site titration
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Title: Quantitative Cu Counting Methodologies for Cu/SSZ-13 Selective Catalytic Reduction Catalysts by Electron Paramagnetic Resonance Spectroscopy

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