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Fast and efficient molecular electrocatalysts for H2 production: Using hydrogenase enzymes as guides

  • Recent Developments in Solar Water-Splitting Photocatalysis
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Abstract

Hydrogen generation using solar energy will require the development of efficient electrocatalysts for proton reduction. This article discusses the important role that proton movement plays in hydrogenase enzymes and potential devices for solar generation. Studies of hydrogenase enzymes provide many important design principles for the development of simpler molecular catalysts. These principles are illustrated with examples from the literature and from the authors’ laboratories. In particular, pendant bases incorporated in the second coordination sphere of catalytic molecules play a number of important roles that are crucial to efficient catalysis. These roles include acting as relays to move protons between the metal center and solution, promoting intra- and intermolecular proton transfer reactions, coupling proton and electron transfer reactions, assisting heterolytic cleavage of hydrogen, and stabilizing critical reaction intermediates. The importance of controlling proton movement on the molecular scale underscores the importance of a similar degree of control in devices designed for the solar production of hydrogen or any fuel generation process involving multiple electrons and protons.

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Acknowledgments

The authors would like to acknowledge support by the Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences and Geosciences of the Department of Energy and by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. The Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

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Authors and Affiliations

  1. Pacific Northwest National Laboratory, Richland, 99352, WA, USA

    Jenny Y Yang, R Morris Bullock, M Rakowski DuBois & Daniel L DuBois

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  1. Jenny Y Yang
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  2. R Morris Bullock
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  3. M Rakowski DuBois
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  4. Daniel L DuBois
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Correspondence to Jenny Y Yang.

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Yang, J., Bullock, R., DuBois, M. et al. Fast and efficient molecular electrocatalysts for H2 production: Using hydrogenase enzymes as guides. MRS Bulletin 36, 39–47 (2011). https://doi.org/10.1557/mrs.2010.8

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