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Nickel-centred proton reduction catalysis in a model of [NiFe] hydrogenase

Nature Chemistry volume 8, pages 1054–1060 (2016)Cite this article

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Abstract

Hydrogen production through water splitting is one of the most promising solutions for the storage of renewable energy. [NiFe] hydrogenases are organometallic enzymes containing nickel and iron centres that catalyse hydrogen evolution with performances that rival those of platinum. These enzymes provide inspiration for the design of new molecular catalysts that do not require precious metals. However, all heterodinuclear NiFe models reported so far do not reproduce the Ni-centred reactivity found at the active site of [NiFe] hydrogenases. Here, we report a structural and functional NiFe mimic that displays reactivity at the Ni site. This is shown by the detection of two catalytic intermediates that reproduce structural and electronic features of the Ni-L and Ni-R states of the enzyme during catalytic turnover. Under electrocatalytic conditions, this mimic displays high rates for H2 evolution (second-order rate constant of 2.5 × 104 M−1 s−1; turnover frequency of 250 s−1 at 10 mM H+ concentration) from mildly acidic solutions.

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Figure 1: Active site and H2 production catalytic cyclic of [NiFe] hydrogenase.
Figure 2: Synthesis and X-ray structure of LN2S2NiIIFeII.
Figure 3: DFT-optimized structures and principal spectroscopic characterizations of LN2S2NiIIFeII, LN2S2NiIFeII and LN2S2NiII(H)FeII.
Figure 4: Electrocatalytic properties for H2 production of LN2S2NiIIFeII.
Figure 5: H2 production catalytic cycle of LN2S2NiIIFeII.

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Acknowledgements

Financial support for this work was provided by Labex arcane (ANR-11-LABX-003), the European Research Council under the European Union's Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement no. 306398 and the COST Action CM1305 (EcostBio) including an STSM grant (COST-STSM-CM1305- 26539) to D.B.

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Author notes

  1. Trevor R. Simmons

    Present address: Present address: Energy Materials Laboratory, University of East Anglia, Norwich Research Park, Norwich, Norfolk NR4 7TJ, UK,

Authors and Affiliations

  1. Univ. Grenoble Alpes, CNRS UMR 5250, DCM, Grenoble, F-38000, France

    Deborah Brazzolotto, Marcello Gennari & Carole Duboc

  2. Univ. Grenoble Alpes, CNRS UMR 5249, CEA, Laboratoire de Chimie et Biologie des Métaux, Grenoble, F-38000, France

    Deborah Brazzolotto, Nicolas Queyriaux, Trevor R. Simmons & Vincent Artero

  3. Univ. Grenoble Alpes, INAC-LCIB, Grenoble, F-38000, France

    Jacques Pécaut

  4. CEA, DRF-INAC-SyMMES, Reconnaissance Ionique et Chimie de Coordination, Grenoble, F-38000, France

    Jacques Pécaut

  5. Institute of Inorganic Chemistry, Georg-August-University Göttingen, Tammannstrasse 4, Göttingen, D-37077, Germany

    Serhiy Demeshko & Franc Meyer

  6. International Center for Advanced Studies of Energy Conversion (ICASEC), Georg-August-University, Göttingen, D-37077, Germany

    Franc Meyer

  7. Institut des Sciences Moléculaires de Marseille, Aix Marseille Université, CNRS, Centrale Marseille, ISM2 UMR 7313, Marseille, 13397, France

    Maylis Orio

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Contributions

C.D. and V.A. conceived and designed the project. D.B. carried out the experimental work under the supervision of M.G. T.R.S. contributed to the synthetic work. J.P. performed X-ray analysis. F.M. and S.D. performed and analysed the Mössbauer experiments. N.Q. contributed to the analysis of the electrochemical data. M.O. carried out the theoretical calculations. C.D., V.A. and M.G. analysed and interpreted the experimental data and prepared the manuscript. All authors reviewed and contributed to the manuscript.

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Correspondence to Vincent Artero or Carole Duboc.

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Crystallographic data for compound LN2S2NiIIFeII. (CIF 1725 kb)

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Brazzolotto, D., Gennari, M., Queyriaux, N. et al. Nickel-centred proton reduction catalysis in a model of [NiFe] hydrogenase. Nature Chem 8, 1054–1060 (2016). https://doi.org/10.1038/nchem.2575

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