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Ethene Dimerization on Zeolite-Hosted Ni Ions: Reversible Mobilization of the Active Site
Rasmus Yding Brogaard1,2, Mustafa Kømurcu1, Michael Martin Dyballa1
1Department of Chemistry, Centre for Materials and Nanoscience (SMN), University of Oslo, P.O. Box 1033, Blindern, NO-0315 Oslo, Norway.
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.
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