A comparative test of different density functionals for calculations of NH<sub>3</sub>-SCR over Cu-Chabazite

Lin, Chen; Janssens, Ton V. W.; Grönbeck, Henrik

doi:10.1039/c9cp01576k

Cited by 54 publications

(77 citation statements)

References 66 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The same framework is also used extensively for the selective catalytic reduction (SCR) of NO x emissions. Here, copper‐exchanged SSZ‐13, Cu‐SSZ‐13, is employed . The second part of our work will focus on the performance of DFT for this redox reaction, where the copper oxidation state shifts between Cu I and Cu II .…”

Section: Figurementioning

confidence: 99%

“…Here, copper-exchanged SSZ-13, Cu-SSZ-13, is employed. [50][51][52][53][54][55][56][57][58][59][60][61][62][63][64][65][66][67][68] The second part of our work will focus on the performance of DFT for this redox reaction, where the copper oxidation state shifts between Cu I and Cu II . [51,52,57,62,[69][70][71][72][73][74][75][76][77] CHA is thus ideally suited as it allows to investigate the performance of DFT for two very distinct problems (acid-base and redox chemistry) using the same framework topology.…”

mentioning

confidence: 99%

See 1 more Smart Citation

On the Accuracy of Density Functional Theory in Zeolite Catalysis

2019

View full text Add to dashboard Cite

Zeolites are porous materials that are typically studied using periodic density functional theory (DFT). In this work we benchmark commonly used density functionals using cluster models for Brønsted acidic as well as copper substituted SSZ‐13 (H‐SSZ‐13 and Cu‐SSZ‐13). We find that for acid‐catalyzed reactions with relevance for the methanol‐to‐olefins process, barriers are the main challenge as they are commonly underestimated by DFT. For reactions involving Cu‐SSZ‐13 (commonly used for the selective catalytic reduction of NOx, SCR), reaction energies are already a challenge for most density functionals. Our results show that the widely used PBE‐D3 functional leads to mean absolute errors larger than 40 kJ/mol for barrier heights. Hybrid functionals show significant improvements with the best tested functional herein M06 having an error of only 7 kJ/mol.

show abstract

Section: Figurementioning

confidence: 99%

mentioning

confidence: 99%

On the Accuracy of Density Functional Theory in Zeolite Catalysis

2019

View full text Add to dashboard Cite

show abstract

“…In zeolites, the van der Waals interaction has been found to be important to include in the functional. Moreover, the Cu-O bond has shown sensitivity to the localization of the 3d-electrons [44]. The effect of using a +U correction of U = 6 eV is shown in Figures S3 and S6 for Z 2 [Cu 2 O] and Z 2 [Cu 2 OH], respectively.…”

Section: Methodsmentioning

confidence: 99%

Reaction Mechanism for Methane-to-Methanol in Cu-SSZ-13: First-Principles Study of the Z2[Cu2O] and Z2[Cu2OH] Motifs

et al. 2020

Self Cite

View full text Add to dashboard Cite

As transportation continues to increase world-wide, there is a need for more efficient utilization of fossil fuel. One possibility is direct conversion of the solution gas bi-product CH4 into an energy-rich, easily usable liquid fuel such as CH3OH. However, new catalytic materials to facilitate the methane-to-methanol reaction are needed. Using density functional calculations, the partial oxidation of methane is investigated over the small-pore copper-exchanged zeolite SSZ-13. The reaction pathway is identified and the energy landscape elucidated over the proposed motifs Z2[Cu2O] and Z2[Cu2OH]. It is shown that the Z2[Cu2O] motif has an exergonic reaction path, provided water is added as a solvent for the desorption step. However, a micro-kinetic model shows that neither Z2[Cu2O] nor Z2[Cu2OH] has any notable activity under the reaction conditions. These findings highlight the importance of the detailed structure of the active site and that the most stable motif is not necessarily the most active.

show abstract

“…It is a known problem that semilocal exchange-correlation functionals delocalize the open spin states over the copper atoms in the system. 43 However, this only has a minor effect on methanol adsorption energies. 44 The silanol was modelled over the monomer silicon T-site from a dissociated water molecule (Figs.…”

Section: Theoretical Methodsmentioning

confidence: 99%

Desorption products during linear heating of copper zeolites with pre-adsorbed methanol

Wang

Arvidsson

Skoglundh

et al. 2020

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

A comparative test of different density functionals for calculations of NH₃-SCR over Cu-Chabazite

Abstract: A general challenge in density functional theory calculations is to simultaneously account for different types of bonds. Here, different exchange–correlation functionals are explored for O2 dissociation over Cu(NH3)2+ complexes in Cu-Chabazite.

Cited by 54 publications

References 66 publications

On the Accuracy of Density Functional Theory in Zeolite Catalysis

On the Accuracy of Density Functional Theory in Zeolite Catalysis

Reaction Mechanism for Methane-to-Methanol in Cu-SSZ-13: First-Principles Study of the Z2[Cu2O] and Z2[Cu2OH] Motifs

Desorption products during linear heating of copper zeolites with pre-adsorbed methanol

Contact Info

Product

Resources

About

A comparative test of different density functionals for calculations of NH3-SCR over Cu-Chabazite

Abstract: A general challenge in density functional theory calculations is to simultaneously account for different types of bonds. Here, different exchange–correlation functionals are explored for O2 dissociation over Cu(NH3)2+ complexes in Cu-Chabazite.

Cited by 54 publications

References 66 publications

On the Accuracy of Density Functional Theory in Zeolite Catalysis

On the Accuracy of Density Functional Theory in Zeolite Catalysis

Reaction Mechanism for Methane-to-Methanol in Cu-SSZ-13: First-Principles Study of the Z2[Cu2O] and Z2[Cu2OH] Motifs

Desorption products during linear heating of copper zeolites with pre-adsorbed methanol

Contact Info

Product

Resources

About

A comparative test of different density functionals for calculations of NH₃-SCR over Cu-Chabazite