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Highly efficient additive-free dehydrogenation of neat formic acid

Nature Catalysis volume 4, pages 193–201 (2021)Cite this article

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Abstract

Formic acid (FA) is a promising hydrogen carrier that can play an instrumental role in the overall implementation of a hydrogen economy. In this regard, it is important to generate H2 gas from neat FA without any solvent and/or additive, for which existing systems are scarce. Here we report the remarkable catalytic activity of a ruthenium 9H-acridine pincer complex for this process. The catalyst is unusually stable and robust in FA, even at high temperatures, and can catalyse neat FA dehydrogenation for over a month, with a total turnover number of 1,701,150. It can also generate high H2/CO2 gas pressures from neat FA (tested up to 100 bars). Mechanistic investigations and density functional theory studies are conducted to fully understand the molecular mechanism of the process. Overall, the high activity, stability, selectivity, simplicity and versatility of the system to generate a CO-free H2/CO2 gas stream and high pressure from neat FA makes it promising for large-scale implementation.

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Fig. 1: Different aspects of the catalytic activity of 1 in the dehydrogenation of neat FA.
Fig. 2: Dehydrogenation of different grades of FA.
Fig. 3: Mechanistic studies.
Fig. 4: Mechanistic cycle.
Fig. 5: DFT-calculated energy profile for FA dehydrogenation catalysed by 1.
Fig. 6: DFT-optimized structure of 1a-fac.
Fig. 7: Comparison of the catalytic activity of 1, 1e and 1-Cl towards neat FA dehydrogenation.

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Data availability

Synthetic procedures, NMR spectra and characterization data for all the new compounds are available within this article and its Supplementary Information. The X-ray crystallographic coordinates for the structure reported in this article have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition number CCDC 2011708. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/structures. DFT-optimized geometries of atomistic models are provided as part of the Supplementary Data. Any further relevant data are available from the authors upon reasonable request.

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Acknowledgements

This research was supported by the European Research Council (ERC AdG 692775). D.M. holds the Israel Matz Professorial Chair of Organic Chemistry. S.K. acknowledges the Sustainability and Energy Research Initiative (SAERI) of the Weizmann Institute of Science for a research fellowship. M.R. acknowledges the Zuckerman STEM Leadership Program for a research fellowship. S.K. thanks M. Montag for useful discussions and for carefully proofreading the manuscript. M.R. thanks N. von Wolff and M. Iron for computational assistance and helpful discussions.

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Authors and Affiliations

  1. Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, Israel

    Sayan Kar, Michael Rauch, Yehoshoa Ben-David & David Milstein

  2. Department of Chemical Research Support, Weizmann Institute of Science, Rehovot, Israel

    Gregory Leitus

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Contributions

D.M. and S.K. conceived and directed the project and designed the experiments. S.K. performed and analysed the experiments. M.R. performed the computational studies and provided important insights regarding reaction mechanisms. G.L. performed experiments and analysed data for the X-ray structure determination. Y.B.-D. synthesized the PNP ligand used in this study. S.K., M.R. and D.M. prepared the manuscript.

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Correspondence to David Milstein.

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Peer review information Nature Catalysis thanks Kuo-Wei Huang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–51, Tables 1–7, Methods, Notes and Discussions.

Supplementary Data 1

Crystallographic data.

Supplementary Data 2

Computational data.

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Kar, S., Rauch, M., Leitus, G. et al. Highly efficient additive-free dehydrogenation of neat formic acid. Nat Catal 4, 193–201 (2021). https://doi.org/10.1038/s41929-021-00575-4

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