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Plasmon-driven carbon–fluorine (C(sp3)–F) bond activation with mechanistic insights into hot-carrier-mediated pathways

Nature Catalysis volume 3, pages 564–573 (2020)Cite this article

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Matters Arising to this article was published on 28 March 2022

Abstract

The activation of carbon–fluorine bonds is an industrially and environmentally critical, but energetically challenging, transformation. Here we demonstrate a plasmonic photocatalysis approach to visible-light-driven hydrodefluorination that utilizes aluminium–palladium antenna–reactor heterostructures. Photocatalytic hydrodefluorination of aliphatic carbon–fluorine (C(sp3)–F) bonds in fluoromethane as a model molecule, in the presence of deuterium, results in the selective production of monodeuterated methane with a remarkable photocatalytic efficiency and stability. Analysis of the reaction kinetics reveals a reduction in the apparent reaction barrier and changes to the deuterium reaction order under illumination, which suggests a non-thermal contribution from photogenerated hot carriers to the reaction pathway. Using embedded correlated wavefunction methods, the ground- and excited-state energetics and the role of plasmon excitation in lowering the reaction barrier and modifying the kinetics under illumination are determined. Plasmon-mediated carbon–fluorine bond activation represents a promising potential for applications in high-value chemical transformations, as well as in abatement technologies for the mitigation of anthropogenic polyfluoroorganic compounds.

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Fig. 1: Plasmon-driven C–F bond activation.
Fig. 2: Photocatalytic characterization of the Al−Pd antenna–reactor for HDF of CH3F.
Fig. 3: Long-term photocatalytic stability.
Fig. 4: Mechanism of the HDF of CH3F.
Fig. 5: Calculated ground- and excited-state energy curves along the minimum energy paths (MEPs).
Fig. 6: Kinetics measurements.

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Data availability

The atomic coordinates for the surface reactions used in the quantum mechanical simulations are provided as Supplementary Data. The data that support the findings of this paper are available from the corresponding authors upon reasonable request.

Code availability

The modified VASP 5.3.3 code subroutines with embedding implementation and associated Python scripts, and the standalone embedding integral generator code used to transform the embedding potential from Cartesian grid to atomic orbital bases, are available via GitHub, https://github.com/EACcodes/VASPEmbedding and https://github.com/EACcodes/EmbeddingIntegralGenerator, respectively, both under the Mozilla Public License 2.0.

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Acknowledgements

This research was financially supported by the Air Force Office of Scientific Research Multidisciplinary Research Program of the University Research Initiative (MURI FA9550-15-1-0022) (E.A.C., P.N. and N.J.H.), DTRA (HDTRA1-16-1-0042) (N.J.H. and P.N.) and the Welch Foundation under grants C-1220 (N.J.H.) and C-1222 (P.N.). H.R. acknowledges the Postdoctoral Fellowship support in Chemical Science by the Arnold and Mabel Beckman Foundation. E.A.C. acknowledges the High Performance Computing Modernization Program (HPCMP) of the US Department of Defense and Princeton University’s Terascale Infrastructure for Groundbreaking Research in Engineering and Science (TIGRESS) for providing computational resources.

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Authors and Affiliations

  1. Department of Electrical and Computer Engineering, Rice University, Houston, TX, USA

    Hossein Robatjazi, Linan Zhou, Peter Nordlander & Naomi J. Halas

  2. Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ, USA

    Hossein Robatjazi, Junwei Lucas Bao & Emily A. Carter

  3. Department of Physics and Astronomy, Rice University, Houston, TX, USA

    Ming Zhang, Peter Nordlander & Naomi J. Halas

  4. Department of Chemical Engineering, University of California, Santa Barbara, CA, USA

    Phillip Christopher

  5. School of Engineering and Applied Science, Princeton University, Princeton, NJ, USA

    Emily A. Carter

  6. Office of the Chancellor and Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, CA, USA

    Emily A. Carter

  7. Department of Chemistry, Rice University, Houston, TX, USA

    Naomi J. Halas

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Contributions

H.R. and N.J.H. designed the project. H.R. performed the photocatalyst synthesis, carried out photocatalytic experiments and analysed the data. H.R. and L.Z. performed the photocatalyst characterizations. J.L.B. carried out the quantum mechanical calculations. M.Z. performed the electromagnetic simulations. P.C. assisted with interpreting the results. H.R. prepared the initial draft of the manuscript with an assist from J.L.B. All the authors discussed the results and contributed to the final manuscript preparation. E.A.C., P.N. and N.J.H. supervised the project.

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Correspondence to Emily A. Carter or Naomi J. Halas.

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Supplementary Information

Supplementary Notes 1–4 and Figs. 1–15.

Supplementary Data

Atomic coordinates for the surface reaction simulations on a palladium Pd(111) slab.

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Robatjazi, H., Bao, J.L., Zhang, M. et al. Plasmon-driven carbon–fluorine (C(sp3)–F) bond activation with mechanistic insights into hot-carrier-mediated pathways. Nat Catal 3, 564–573 (2020). https://doi.org/10.1038/s41929-020-0466-5

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