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Critical role of solvent-modulated hydrogen-binding strength in the catalytic hydrogenation of benzaldehyde on palladium

Nature Catalysis volume 4, pages 976–985 (2021)Cite this article

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Abstract

Solvents not only disperse reactants to enhance mass transport in catalytic reactions but also alter the reaction kinetically. Here, we show that the rate of benzaldehyde hydrogenation on palladium differs by up to one order of magnitude in different solvents (dioxane < tetrahydrofuran < water < methanol). However, the reaction pathway does not change; the majority of turnovers occurs by stepwise addition of sorbed hydrogen to sorbed benzaldehyde, first to the carbonyl oxygen and then to the carbon atom of the formyl group, forming benzyl alcohol. An analysis of the solvation energies shows that both ground and transition states are destabilized by the solvents compared to those at the gas–solid interface. The destabilization extent of the reacting organic substrates in both states are similar and, therefore, compensate each other, making the net kinetic effects inconsequential. Instead, the marked reactivity differences arise only from the differences in the solvation of sorbed hydrogen.

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Fig. 1: Schematic illustration of catalytic cycle for benzaldehyde hydrogenation.
Fig. 2: Deuterated products in the hydrogenation of benzaldehyde.
Fig. 3: Standard free energy profile of the benzaldehyde hydrogenation.
Fig. 4: Dependence of reaction barrier on sorbed hydrogen or sorbed benzaldehyde.

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All data are available within the paper and its Supplementary Information files or from the corresponding authors upon request.

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Acknowledgements

G.C. is grateful to the Chinese Scholarship Council for the financial support. J.A.L. and O.Y.G. acknowledge the support by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences and Biosciences (Transdisciplinary Approaches to Realize Novel Catalytic Pathways to Energy Carriers, FWP 47319). Y.-H.(C.)C. acknowledges support from the Alexander von Humboldt Foundation which enabled the interaction in this research. We further thank F.-X. Hecht for technical support concerning the construction of the experimental set-up.

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Authors and Affiliations

  1. Department of Chemistry and Catalysis Research Center, Technische Universität München, Garching, Germany

    Guanhua Cheng, Andreas Jentys, Yue Liu, Ya-Huei (Cathy) Chin & Johannes A. Lercher

  2. Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, WA, USA

    Oliver Y. Gutiérrez & Johannes A. Lercher

  3. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, PR China

    Yue Liu

  4. Department of Chemical Engineering and Applied Chemistry, University of Toronto, Toronto, Ontario, Canada

    Ya-Huei (Cathy) Chin

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  1. Guanhua Cheng
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Contributions

G.C. carried out the reactions and performed the characterizations for selected materials. A.J. and O.Y.G. cooperated with the discussion and provided valuable suggestions. Y.-H.(C.)C. planned the kinetic experiments and analysed the rate data. Y.L. and J.A.L. supervised the work and provided guidance throughout the project. All the coauthors contributed to the discussion and helped to revise the manuscript.

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Correspondence to Yue Liu, Ya-Huei (Cathy) Chin or Johannes A. Lercher.

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Peer review information Nature Catalysis thanks Raghunath Chaudhari, Guichang Wang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary methods, Figs. 1–16, Notes 1–4 and Tables 1–5.

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Cheng, G., Jentys, A., Gutiérrez, O.Y. et al. Critical role of solvent-modulated hydrogen-binding strength in the catalytic hydrogenation of benzaldehyde on palladium. Nat Catal 4, 976–985 (2021). https://doi.org/10.1038/s41929-021-00701-2

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