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Tandem copper hydride–Lewis pair catalysed reduction of carbon dioxide into formate with dihydrogen

Nature Catalysis volume 1, pages 743–747 (2018)Cite this article

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Abstract

The reduction of CO2 into formic acid or its conjugate base, using dihydrogen, is an attractive process. While catalysts based on noble metals have shown high turnover numbers, the use of abundant first-row metals is underdeveloped. The key steps of the reaction are CO2 insertion into a metal hydride and regeneration of the metal hydride with H2, along with the concomitant production of formate. For the first step, copper is known as one of the most efficient metals, as shown by the numerous copper-catalysed carboxylation reactions, but this metal has difficulties activating H2 to achieve the second step. Here, we report a catalytic system involving a stable copper hydride that activates CO2, working in tandem with a Lewis pair that heterolytically splits H2. In this system, unprecedented turnover numbers for copper are obtained. Surprisingly, through a combination of stoichiometric and catalytic reactions, we show that classical Lewis pairs outperform frustrated Lewis pairs in this process.

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Fig. 1: Limitations to the copper- and FLP-catalysed reduction of CO2 with H2.
Fig. 2: Stoichiometric reactions supporting our working hypothesis.
Fig. 3: Stoichiometric reactivity of the DBU/BCF Lewis pair with H2 and CO2.
Fig. 4: Stoichiometric reactions supporting the proposed catalytic cycle.

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Data availability

CCDC 1839096 (B1), 1839093 (\({\mathbf{C}}_{\mathbf{1}}^{{\rm{C}}_{6}{\rm{F}}_{5}}\)), 1839094 (C3H) and 1839095 (3) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre. All other data are available from the authors upon reasonable request.

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Acknowledgements

This work was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Catalysis Science Program, under award number DE-SC0009376, Solvay and the NNSF of China (numbers 21676134 and 21576129). We gratefully acknowledge support from the US Department of Education for a GAANN fellowship (E.A.R.) and the Japan Society for the Promotion of Science for a Postdoctoral Fellowship for Study Abroad (R.N.).

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Author notes

  1. These authors contributed equally: Erik A. Romero, Tianxiang Zhao.

Authors and Affiliations

  1. UCSD-CNRS Joint Research Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA, USA

    Erik A. Romero, Ryo Nakano, Rodolphe Jazzar & Guy Bertrand

  2. Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China

    Tianxiang Zhao, Xingbang Hu & Youting Wu

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Contributions

E.A.R., R.N. and R.J. performed the stoichiometric experiments, mechanistic studies and X-ray crystallographic analyses. R.J. and G.B. developed the synergistic mechanism. T.Z. and X.H. performed the catalytic studies. X.H. and Y.W. developed the catalytic conditions for the reduction of CO2 using CAACCuBH4. All authors discussed the results and wrote the paper.

Corresponding authors

Correspondence to Xingbang Hu, Rodolphe Jazzar or Guy Bertrand.

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Supplementary Information

Supplementary Information

Supplementary Methods, Supplementary Figures 1–13, Supplementary Tables 1–4, Supplementary References

Compound 3

Crystallographic data for compound 3

Compound B1

Crystallographic data for compound B1

Compound C1C6F5

Crystallographic data for compound C1C6F5

Compound C3H

Crystallographic data for compound C3H

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Romero, E.A., Zhao, T., Nakano, R. et al. Tandem copper hydride–Lewis pair catalysed reduction of carbon dioxide into formate with dihydrogen. Nat Catal 1, 743–747 (2018). https://doi.org/10.1038/s41929-018-0140-3

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