| 1. |
- Chen, Lin, 1990, et al.
(författare)
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A comparative test of different density functionals for calculations of NH3-SCR over Cu-Chabazite
- 2019
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Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9084 .- 1463-9076. ; 21:21, s. 10923-10930
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Tidskriftsartikel (refereegranskat)abstract
- A general challenge in density functional theory calculations is to simultaneously account for different types of bonds. One such example is reactions in zeolites where both van der Waals and chemical bonds should be described accurately. Here, we use different exchange-correlation functionals to explore O2 dissociation over pairs of Cu(NH3)2+ complexes in Cu-Chabazite. This is an important part of selective catalytic reduction of NOx using NH3 as a reducing agent. The investigated functionals are PBE, PBE+U, PBE+D, PBE+U+D, PBE-cx, BEEF and HSE06+D. We find that the potential energy landscape for O2 activation and dissociation depends critically on the choice of functional. However, the van der Waals contributions are similarly described by the functionals accounting for this interaction. The discrepancies in the potential energy surface are instead related to different descriptions of the Cu-O chemical bond. By investigating the electronic, structural and energetic properties of reference systems including bulk copper oxides and (Cu2O2)2+ enzymatic crystals, we find that the PBE+U approach together with van der Waals corrections provides a reasonable simultaneous accuracy of the different bonds in the systems.
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| 2. |
- Chen, Lin, 1990, et al.
(författare)
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Interpretation of NH 3 -TPD Profiles from Cu-CHA Using First-Principles Calculations
- 2019
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Ingår i: Topics in Catalysis. - : Springer Science and Business Media LLC. - 1572-9028 .- 1022-5528. ; 62:1-4, s. 93-99
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Tidskriftsartikel (refereegranskat)abstract
- Temperature-programmed desorption (TPD) with ammonia is widely used for zeolite characterization revealing information on acidity and adsorption sites. The interpretation of TPD measurements is, however, often challenging. One example is the NH 3 -TPD profile from Cu-chabazite (Cu-CHA) which generally is deconvoluted in three peaks with contributions from NH 3 on Lewis acid sites, copper sites and Brønsted acid sites. Here, we use density functional theory calculations combined with kinetic simulations to analyze this case. We find a large number of possible species, giving rise to overlapping features in the NH 3 -TPD. The experimental low-temperature peak (below 200∘C) is assigned to NH 3 desorption from Lewis acid sites together with NH 3 desorption from a [Cu(II)(OH)(NH3)3]+ complex. The intermediate-temperature peak (250-350∘C) is attributed to decomposition of a linear [Cu(I)(NH3)2]+ complex and a residual from [Cu(II)(OH)(NH3)3]+. The high-temperature peak is predicted to have contributions from Brønsted acid sites (NH4+), [Cu(I)NH3]+ and [Cu(II)(NH3)4]2+. The present work shows that NH 3 -TPD from Cu-CHA can be reconciled with copper complexes as NH 3 storage sites.
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