Ethene dimerization on zeolite-hosted Ni ions : reversible mobilization of the active site
- Author
- Rasmus Yding Brogaard, Mustafa Kømurcu, Michael Martin Dyballa, Alexandru Botan, Veronique Van Speybroeck (UGent) , Unni Olsbye and Kristof De Wispelaere (UGent)
- Organization
- Project
-
- DYNPOR (First principle molecular dynamics simulations for complex chemical transformations in nanoporous materials)
- Abstract
- The active site in ethene oligomerization catalyzed by Ni-zeolites is proposed to be a mobile Ni(II) complex, based on density functional theory-based molecular dynamics (DFT-MD) simulations corroborated by continuous-flow experiments on Ni-SSZ-24 zeolite. The results of the simulations at operating conditions show that ethene molecules reversibly mobilize the active site as they exchange with the zeolite as ligands on Ni during reaction. Microkinetic modeling was conducted on the basis of free-energy profiles derived with DFT-MD for oligomerization on these mobile [(ethene)(2)-Ni-alkyl](+) species. The model reproduces the experimentally observed high selectivity to dimerization and indicates that the mechanism is consistent with the observed second-order rate dependence on ethene pressure.
- Keywords
- adsorption, host-guest systems, molecular dynamics, agostic interactions, alkene oligomerization, homogeneous catalysis, GENERALIZED GRADIENT APPROXIMATION, OLEFIN OLIGOMERIZATION, ETHYLENE DIMERIZATION, CATALYSTS
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Citation
Please use this url to cite or link to this publication: http://hdl.handle.net/1854/LU-8625335
- MLA
- Brogaard, Rasmus Yding, et al. “Ethene Dimerization on Zeolite-Hosted Ni Ions : Reversible Mobilization of the Active Site.” ACS CATALYSIS, vol. 9, no. 6, 2019, pp. 5645–50, doi:10.1021/acscatal.9b00721.
- APA
- Brogaard, R. Y., Kømurcu, M., Dyballa, M. M., Botan, A., Van Speybroeck, V., Olsbye, U., & De Wispelaere, K. (2019). Ethene dimerization on zeolite-hosted Ni ions : reversible mobilization of the active site. ACS CATALYSIS, 9(6), 5645–5650. https://doi.org/10.1021/acscatal.9b00721
- Chicago author-date
- Brogaard, Rasmus Yding, Mustafa Kømurcu, Michael Martin Dyballa, Alexandru Botan, Veronique Van Speybroeck, Unni Olsbye, and Kristof De Wispelaere. 2019. “Ethene Dimerization on Zeolite-Hosted Ni Ions : Reversible Mobilization of the Active Site.” ACS CATALYSIS 9 (6): 5645–50. https://doi.org/10.1021/acscatal.9b00721.
- Chicago author-date (all authors)
- Brogaard, Rasmus Yding, Mustafa Kømurcu, Michael Martin Dyballa, Alexandru Botan, Veronique Van Speybroeck, Unni Olsbye, and Kristof De Wispelaere. 2019. “Ethene Dimerization on Zeolite-Hosted Ni Ions : Reversible Mobilization of the Active Site.” ACS CATALYSIS 9 (6): 5645–5650. doi:10.1021/acscatal.9b00721.
- Vancouver
- 1.Brogaard RY, Kømurcu M, Dyballa MM, Botan A, Van Speybroeck V, Olsbye U, et al. Ethene dimerization on zeolite-hosted Ni ions : reversible mobilization of the active site. ACS CATALYSIS. 2019;9(6):5645–50.
- IEEE
- [1]R. Y. Brogaard et al., “Ethene dimerization on zeolite-hosted Ni ions : reversible mobilization of the active site,” ACS CATALYSIS, vol. 9, no. 6, pp. 5645–5650, 2019.
@article{8625335,
abstract = {{The active site in ethene oligomerization catalyzed by Ni-zeolites is proposed to be a mobile Ni(II) complex, based on density functional theory-based molecular dynamics (DFT-MD) simulations corroborated by continuous-flow experiments on Ni-SSZ-24 zeolite. The results of the simulations at operating conditions show that ethene molecules reversibly mobilize the active site as they exchange with the zeolite as ligands on Ni during reaction. Microkinetic modeling was conducted on the basis of free-energy profiles derived with DFT-MD for oligomerization on these mobile [(ethene)(2)-Ni-alkyl](+) species. The model reproduces the experimentally observed high selectivity to dimerization and indicates that the mechanism is consistent with the observed second-order rate dependence on ethene pressure.}},
author = {{Brogaard, Rasmus Yding and Kømurcu, Mustafa and Dyballa, Michael Martin and Botan, Alexandru and Van Speybroeck, Veronique and Olsbye, Unni and De Wispelaere, Kristof}},
issn = {{2155-5435}},
journal = {{ACS CATALYSIS}},
keywords = {{adsorption,host-guest systems,molecular dynamics,agostic interactions,alkene oligomerization,homogeneous catalysis,GENERALIZED GRADIENT APPROXIMATION,OLEFIN OLIGOMERIZATION,ETHYLENE DIMERIZATION,CATALYSTS}},
language = {{eng}},
number = {{6}},
pages = {{5645--5650}},
title = {{Ethene dimerization on zeolite-hosted Ni ions : reversible mobilization of the active site}},
url = {{http://doi.org/10.1021/acscatal.9b00721}},
volume = {{9}},
year = {{2019}},
}
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