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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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.
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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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.
The authors declare no competing interests.
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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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