期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 138, 期 18, 页码 6028-6048出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b02651
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资金
- National Science Foundation GOALI program [1258715-CBET, 1258690-CBET]
- Patrick and Jane Eilers Graduate Student Fellowship
- U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences [DE-AC02-06CH11357]
- Office of Biological and Environmental Research
- Div Of Chem, Bioeng, Env, & Transp Sys
- Directorate For Engineering [1258717, 1258690] Funding Source: National Science Foundation
- Div Of Chem, Bioeng, Env, & Transp Sys
- Directorate For Engineering [1258715] Funding Source: National Science Foundation
The relationships among the macroscopic compositional parameters of a Cu-exchanged SSZ-13 zeolite catalyst, the types and numbers of Cu active sites, and activity for the selective catalytic reduction (SCR) of NOx with NH3 are established through experimental interrogation and computational analysis Of materials across the catalyst composition space. Density functional theory, stochastic models, and experimental characterizations demonstrate that within the synthesis protocols applied here and across Si:Al ratios, the volumetric density of six-membered-rings (6MR) containing two Al (2Al sites) is consistent with a random Al siting in the SSZ-13 lattice subject to Lowenstein's rule. Further, exchanged Cu-II ions first populate these 2Al sites before populating remaining unpaired, or 1Al, sites as (CuOH)-O-II. These sites are distinguished and enumerated ex situ;through vibrational and X-ray absorption spectroscopies (XAS) and,chemical titrations. In situ and operando XAS follow Cu oxidation state and coordination environment as a function of environmental,conditions including low-temperature :(473 K) SCR catalysis and are rationalized through first-principles thermodynamics and ab initio molecular dynamics. Experiment and theory together reveal that the Cu sites respond sensitively to exposure conditions, and it particular that Cu species are solvated and mobilized by NH3 under SCR conditions. While Cu sites are spectroscopically and chemically distinct away from these conditions, they exhibit similar turnover rates, apparent activation energies and apparent reaction orders at the SCR conditions, even on zeolite frameworks other than SSZ13.
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