The Electronic States of Rhenium Bipyridyl Electrocatalysts for CO2 Reduction as Revealed by X-ray Absorption Spectroscopy and Computational Quantum Chemistry

Authors

  • Dr. Eric E. Benson,

    1. Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive,Code 0358, La Jolla, CA 92093-0358 (USA)
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    • These authors contributed equally to this work.

  • Matthew D. Sampson,

    1. Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive,Code 0358, La Jolla, CA 92093-0358 (USA)
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    • These authors contributed equally to this work.

  • Dr. Kyle A. Grice,

    1. Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive,Code 0358, La Jolla, CA 92093-0358 (USA)
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  • Dr. Jonathan M. Smieja,

    1. Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive,Code 0358, La Jolla, CA 92093-0358 (USA)
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  • Jesse D. Froehlich,

    1. Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive,Code 0358, La Jolla, CA 92093-0358 (USA)
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  • Dr. Daniel Friebel,

    1. SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA 94025 (USA)
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  • Dr. John A. Keith,

    1. Department of Mechanical and Aerospace Engineering, Princeton University, D404A Engineering Quadrangle, Princeton, NJ 08544 (USA)
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  • Prof. Dr. Emily A. Carter,

    1. Department of Mechanical and Aerospace Engineering, Princeton University, D404A Engineering Quadrangle, Princeton, NJ 08544 (USA)
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  • Prof. Dr. Anders Nilsson,

    1. SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA 94025 (USA)
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  • Prof. Dr. Clifford P. Kubiak

    Corresponding author
    1. Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive,Code 0358, La Jolla, CA 92093-0358 (USA)
    • Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive,Code 0358, La Jolla, CA 92093-0358 (USA)
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  • This material is based upon work supported by the Air Force Office of Scientific Research through the MURI program under AFOSR Award No. FA9550-10-1-0572. This research was partly carried out at the Stanford Synchrotron Radiation Lightsource, a National User Facility operated by Stanford University on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences. We thank John Bargar, Matthew Latimer, Erik Nelson, and Juan Lezama Pacheco for their support of the X-ray Absorption Spectroscopy experiments. We also thank Dr. Arnold Rheingold and Dr. Curtis Moore for their assistance with the single crystal XRD experiments.

Abstract

original image

Where are the electrons that allow a highly reduced rhenium bipyridyl catalyst to attack CO2, but not H+? XAS and computational quantum chemistry indicate that the negative charge in [Re(bpy)(CO)3] and [Re(bpy-tBu)(CO)3] is not stored in a localized Re 5d state, but rather in the bipyridine ligand . The active states of this family of catalysts possess formally Re0 metal centers with singly reduced bipyridine ligands.

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