Probing the Interactions of Immobilized Ruthenium Dihydride Complexes with Metal Oxide Surfaces by MAS NMR: Effects on CO2 Hydrogenation

H.-H. Nguyen, Z. Li, T. Enenkel, J. Hildebrand, M. Bauer, M. Dyballa, D.P. Estes, The Journal of Physical Chemistry C 125 (2021) 14627–14635.

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Journal Article | Published | English
Author
Nguyen, Hoang-Huy; Li, Zheng; Enenkel, Toni; Hildebrand, Joachim; Bauer, MatthiasLibreCat ; Dyballa, Michael; Estes, Deven P.
Abstract
Homogeneous catalysts immobilized on metal oxides often have different catalytic properties than in homogeneous solution. This can be either activating or deactivating and is often attributed to interactions of catalyst species with the metal oxide surface. However, few studies have ever demonstrated the effect that close associations of active sites with surfaces have on the catalytic activity. In this paper, we immobilize H2Ru(PPh3)2(Ph2P)2N–C3H6–Si(OEt)3 (3) on SiO2, Al2O3, and ZnO and interrogate the relationship to the surface using IR, MAS NMR, 1H–31P HETCOR, and XAS spectroscopies. We found that while there are close contacts between the P atoms of the complex and all three metal oxide surfaces, the Ru–H bond only reacts with oxygen bridges on SiO2 and Al2O3, forming new Ru–O bonds. In contrast, complex 3 stays intact on ZnO. Comparison of the catalytic activities of our immobilized species for CO2 hydrogenation to ethyl formate showed that Lewis acidic metal oxides activate, rather than deactivate, complex 3 in the order Al2O3 > ZnO > SiO2. The Lewis acidic sites on the metal oxide surfaces most likely increase the productivity by increasing the rate of esterification of formate intermediates.
Publishing Year
Journal Title
The Journal of Physical Chemistry C
Volume
125
Issue
27
Page
14627-14635
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Cite this

Nguyen H-H, Li Z, Enenkel T, et al. Probing the Interactions of Immobilized Ruthenium Dihydride Complexes with Metal Oxide Surfaces by MAS NMR: Effects on CO2 Hydrogenation. The Journal of Physical Chemistry C. 2021;125(27):14627-14635. doi:10.1021/acs.jpcc.1c02074
Nguyen, H.-H., Li, Z., Enenkel, T., Hildebrand, J., Bauer, M., Dyballa, M., & Estes, D. P. (2021). Probing the Interactions of Immobilized Ruthenium Dihydride Complexes with Metal Oxide Surfaces by MAS NMR: Effects on CO2 Hydrogenation. The Journal of Physical Chemistry C, 125(27), 14627–14635. https://doi.org/10.1021/acs.jpcc.1c02074
@article{Nguyen_Li_Enenkel_Hildebrand_Bauer_Dyballa_Estes_2021, title={Probing the Interactions of Immobilized Ruthenium Dihydride Complexes with Metal Oxide Surfaces by MAS NMR: Effects on CO2 Hydrogenation}, volume={125}, DOI={10.1021/acs.jpcc.1c02074}, number={27}, journal={The Journal of Physical Chemistry C}, publisher={American Chemical Society (ACS)}, author={Nguyen, Hoang-Huy and Li, Zheng and Enenkel, Toni and Hildebrand, Joachim and Bauer, Matthias and Dyballa, Michael and Estes, Deven P.}, year={2021}, pages={14627–14635} }
Nguyen, Hoang-Huy, Zheng Li, Toni Enenkel, Joachim Hildebrand, Matthias Bauer, Michael Dyballa, and Deven P. Estes. “Probing the Interactions of Immobilized Ruthenium Dihydride Complexes with Metal Oxide Surfaces by MAS NMR: Effects on CO2 Hydrogenation.” The Journal of Physical Chemistry C 125, no. 27 (2021): 14627–35. https://doi.org/10.1021/acs.jpcc.1c02074.
H.-H. Nguyen et al., “Probing the Interactions of Immobilized Ruthenium Dihydride Complexes with Metal Oxide Surfaces by MAS NMR: Effects on CO2 Hydrogenation,” The Journal of Physical Chemistry C, vol. 125, no. 27, pp. 14627–14635, 2021, doi: 10.1021/acs.jpcc.1c02074.
Nguyen, Hoang-Huy, et al. “Probing the Interactions of Immobilized Ruthenium Dihydride Complexes with Metal Oxide Surfaces by MAS NMR: Effects on CO2 Hydrogenation.” The Journal of Physical Chemistry C, vol. 125, no. 27, American Chemical Society (ACS), 2021, pp. 14627–35, doi:10.1021/acs.jpcc.1c02074.

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