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Ambient conversion of CO2 to hydrocarbons by biogenic and synthetic [Fe4S4] clusters

Nature Catalysis volume 1, pages 444–451 (2018)Cite this article

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Abstract

The Fe protein of nitrogenase contains a redox active [Fe4S4] cluster that plays a key role in electron transfer and substrate reduction. Here we show that the Fe protein of Methanosarcina acetivorans can reduce CO2 and CO to hydrocarbons under ambient conditions. Further, we demonstrate that this reactivity is inherent to [Fe4S4] clusters, showing the ability of a synthetic [Fe4S4] compound to catalyse the same ambient reaction in solutions. Theoretical calculations suggest a reaction mechanism involving an aldehyde-like intermediate that gives rise to hydrocarbon products upon proton-coupled electron transfer and concomitant removal of water molecules. These results provide a framework for mechanistic investigations of FeS-based activation and reduction of CO2 and CO while facilitating potential development of FeS catalysts capable of ambient conversion of CO2 and CO into fuel products.

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Fig. 1: Reduction of CO2 and CO by protein-bound [Fe4S4] clusters.
Fig. 2: Formation of hydrocarbons by protein-bound and synthetic [Fe4S4] clusters.
Fig. 3: Proposed reaction pathway of CO2 reduction catalysed by the [Fe4S4] cluster.
Fig. 4: Alternative reaction pathway of CO2 reduction catalysed by the [Fe4S4] cluster.
Fig. 5: Reduction of CH2O to CH4 by the synthetic [Fe4S4] cluster.

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Acknowledgements

We thank M. Ribbe (UCI) for helpful discussions. This work was supported by NSF CAREER grant CHE-1651398 (to Y.H.), a grant-in-aid for scientific research (16H04116) from the Japanese Ministry of Education, Culture, Sports, Science and Technology (MEXT), Hori Sciences and Arts Foundation grant, and Takeda Science Foundation grant (to Y.O.).

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  1. These authors contributed equally: Martin T. Stiebritz, Caleb J. Hiller, Nathaniel S. Sickerman and Chi Chung Lee.

Authors and Affiliations

  1. Department of Molecular Biology and Biochemistry, University of California, Irvine, CA, USA

    Martin T. Stiebritz, Caleb J. Hiller, Nathaniel S. Sickerman, Chi Chung Lee, Kazuki Tanifuji & Yilin Hu

  2. Department of Chemistry, University of California, Irvine, CA, USA

    Caleb J. Hiller

  3. Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Japan

    Yasuhiro Ohki

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Y.H. planned the research, M.T.S., C.J.H., N.S.S., C.C.L., K.T., and Y.O. performed the experiments, and Y.H. prepared the manuscript with suggestions of Y.O.

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Correspondence to Yilin Hu.

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Stiebritz, M.T., Hiller, C.J., Sickerman, N.S. et al. Ambient conversion of CO2 to hydrocarbons by biogenic and synthetic [Fe4S4] clusters. Nat Catal 1, 444–451 (2018). https://doi.org/10.1038/s41929-018-0079-4

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