Understanding ammonia selective catalytic reduction kinetics over Cu-SSZ-13 from motion of the Cu ions
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 by 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.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1166833
- Report Number(s):
- PNNL-SA-101081; 47953; VT0401000
- Journal Information:
- Journal of Catalysis, 319:1-14, Journal Name: Journal of Catalysis, 319:1-14
- Country of Publication:
- United States
- Language:
- English
Similar Records
Synthesis and Evaluation of Cu-SAPO-34 Catalysts for Ammonia Selective Catalytic Reduction. 1. Aqueous Solution Ion Exchange
Effects of Si/Al Ratio on Cu/SSZ-13 NH3-SCR Catalysts: Implications for the active Cu species and the Roles of Brønsted Acidity