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Title: Selective Catalytic Reduction over Cu/SSZ-13: Linking Homo- and Heterogeneous Catalysis

Abstract

Active centers in Cu/SSZ-13 selective catalytic reduction (SCR) catalysts have been recently identified as isolated Cu2+ and [CuII(OH)]+ ions. A redox reaction mechanism has also been established, where Cu-ions cycle between CuI and CuII oxidation states during SCR reaction. While the mechanism for the reduction half-cycle (CuII CuI) is reasonably well understood, that for the oxidation half-cycle (CuI CuII) remains an unsettled debate. Herein we report detailed reaction kinetics on low-temperature standard NH3-SCR, supplemented by DFT calculations, as strong evidence that the low-temperature oxidation half-cycle occurs with the participation of two isolated CuI ions, via formation of a transient [CuI(NH3)2]+-O2-[CuI(NH3)2]+ intermediate. The feasibility of this reaction mechanism is confirmed from DFT calculations, and the simulated energy barrier and rate constants are consistent with experimental findings. Significantly, the low-temperature standard SCR mechanism proposed here provides full consistency with low-temperature SCR kinetics. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest Nationalmore » Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.« less

Authors:
ORCiD logo; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1369506
Report Number(s):
PNNL-SA-123327
Journal ID: ISSN 0002-7863; 47953; VT0401000
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 139; Journal Issue: 13
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; selective catalytic reduction; Cu/SSZ-13; reaction mechanism; reaction kinetics; Environmental Molecular Sciences Laboratory

Citation Formats

Gao, Feng, Mei, Donghai, Wang, Yilin, Szanyi, János, and Peden, Charles H. F. Selective Catalytic Reduction over Cu/SSZ-13: Linking Homo- and Heterogeneous Catalysis. United States: N. p., 2017. Web. doi:10.1021/jacs.7b01128.
Gao, Feng, Mei, Donghai, Wang, Yilin, Szanyi, János, & Peden, Charles H. F. Selective Catalytic Reduction over Cu/SSZ-13: Linking Homo- and Heterogeneous Catalysis. United States. doi:10.1021/jacs.7b01128.
Gao, Feng, Mei, Donghai, Wang, Yilin, Szanyi, János, and Peden, Charles H. F. Tue . "Selective Catalytic Reduction over Cu/SSZ-13: Linking Homo- and Heterogeneous Catalysis". United States. doi:10.1021/jacs.7b01128.
@article{osti_1369506,
title = {Selective Catalytic Reduction over Cu/SSZ-13: Linking Homo- and Heterogeneous Catalysis},
author = {Gao, Feng and Mei, Donghai and Wang, Yilin and Szanyi, János and Peden, Charles H. F.},
abstractNote = {Active centers in Cu/SSZ-13 selective catalytic reduction (SCR) catalysts have been recently identified as isolated Cu2+ and [CuII(OH)]+ ions. A redox reaction mechanism has also been established, where Cu-ions cycle between CuI and CuII oxidation states during SCR reaction. While the mechanism for the reduction half-cycle (CuII CuI) is reasonably well understood, that for the oxidation half-cycle (CuI CuII) remains an unsettled debate. Herein we report detailed reaction kinetics on low-temperature standard NH3-SCR, supplemented by DFT calculations, as strong evidence that the low-temperature oxidation half-cycle occurs with the participation of two isolated CuI ions, via formation of a transient [CuI(NH3)2]+-O2-[CuI(NH3)2]+ intermediate. The feasibility of this reaction mechanism is confirmed from DFT calculations, and the simulated energy barrier and rate constants are consistent with experimental findings. Significantly, the low-temperature standard SCR mechanism proposed here provides full consistency with low-temperature SCR kinetics. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.},
doi = {10.1021/jacs.7b01128},
journal = {Journal of the American Chemical Society},
number = 13,
volume = 139,
place = {United States},
year = {Tue Mar 21 00:00:00 EDT 2017},
month = {Tue Mar 21 00:00:00 EDT 2017}
}
  • Cu-SSZ-13 catalysts with three Si/Al ratios, at 6, 12 and 35, are synthesized with solution ion exchange. Catalysts are characterized with surface area/pore volume measurements, temperature programmed reduction (TPR), and electron paramagnetic resonance (EPR) spectroscopy. Catalytic properties are examined using NO oxidation, ammonia oxidation, and standard ammonia selective catalytic reduction (NH3-SCR) reactions. By varying Si/Al ratios and Cu loadings, it is possible to synthesize catalysts with one dominant type of isolated Cu2+ ion species. Prior to full dehydration of the zeolite catalyst, hydrated Cu2+ ions are found to be very mobile as judged from EPR. NO oxidation is catalyzed bymore » O-bridged Cu-dimer species that form at relatively high Cu loadings and in the presence of O2. For NH3 oxidation and standard SCR reactions, transient Cu-dimers even form at much lower Cu loadings; and these are proposed to be the active sites for reaction temperatures ≤ 350 °C. These dimer species can be viewed as in equilibrium with monomeric Cu ion complexes. Between ~250 and 350 °C, these moieties become less stable causing SCR reaction rates to decrease. At temperatures above 350 °C and at low Cu loadings, Cu-dimers completely dissociate to regenerate isolated Cu2+ monomers that then locate at ion-exchange sites of the zeolite lattice. At low Cu loadings, these Cu species are the high-temperature active SCR catalytic centers. At high Cu loadings, on the other hand, both Cu-dimers and monomers are highly active in the high temperature kinetic regime, yet Cu-dimers are less selective in SCR. Brönsted acidity is also very important for SCR reactivity in the high-temperature regime. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.« less
  • The effect of Cu loading on the selective catalytic reduction of NOx by NH3 was examined over 20-80% ion-exchanged Cu-SSZ-13 zeolite catalysts. High NO reduction efficiency (80-95%) was obtained over all catalyst samples between 250 and 500°C, and the gas hourly space velocity of 200,000 h-1. Both NO reduction and NH3 oxidation activities under these conditions were found to increase slightly with increasing Cu loading at low temperatures. However, NO reduction activity was suppressed with increasing Cu loadings at high temperatures (>500oC) due to excess NH3 oxidation. The optimum Cu ion exchange level appears to be ~40-60% as higher thanmore » 80% NO reduction efficiency was obtained over 50% Cu ion-exchanged SSZ-13 up to 600oC. The NO oxidation activity of Cu-SSZ-13 was found to be low regardless of Cu loading, although it was somewhat improved with increasing Cu ion exchange level at high temperatures. During the “fast” SCR (i.e., NO/NO2 =1), only a slight improvement in NOx reduction activity was obtained for Cu-SSZ-13. Regardless of Cu loading, near 100% selectivity to N2 was observed; only a very small amount of N2O was produced even in the presence of NO2. Based on the Cu loading, the apparent activation energies for NO oxidation and NO SCR were estimated to be ~58 kJ/mol and ~41 kJ/mol, respectively.« less
  • A novel solid state method was developed to synthesize Cu-SSZ-13 catalysts with excellent NH3-SCR performance and durable hydrothermal stability. After the solid state ion exchange (SSIE) process, the SSZ framework structure and surface area was maintained. In-situ DRIFTS and NH3-TPD experiments provide evidence that isolated Cu ions were successfully exchanged into the pores, which are the active centers for the NH3-SCR reaction.
  • Superior activity and selectivity of a Cu ion-exchanged SSZ-13 zeolite in the selective catalytic reduction (SCR) of NOx with NH3 were observed, in comparison to Cu-beta and Cu-ZSM-5 zeolites. Cu-SSZ-13 was not only more active in the NOx SCR reaction over the entire temperature range studied (up to 550 °C), but also more selective toward nitrogen formation, resulting in significantly lower amounts of NOx by-products (i.e., NO2 and N2O) than the other two zeolites. In addition, Cu-SSZ-13 demonstrated the highest activity and N2 formation selectivity in the oxidation of NH3. The results of this study strongly suggest that Cu-SSZ-13 ismore » a promising candidate as a catalyst for NOx SCR with great potential in after-treatment systems for either mobile or stationary sources.« less
  • Operando X-ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu-exchanged SSZ-13. Catalysts prepared to contain only isolated, exchanged CuII ions evidence both CuII and CuI ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for CuII reduction to CuI. DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed CuII reduction. The calculations predict in situ generation of Brønsted sites proximal to CuI uponmore » reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of CuI to CuII, which DFT suggests to occur by a NO2 intermediate. Reaction of Cu-bound NO2 with proximal NH4 + completes the catalytic cycle. N2 is produced in both reduction and oxidation half-cycles.« less