Abstract
The overconsumption of single-use plastics is creating a global waste catastrophe, with widespread environmental, economic and health-related consequences. Here we show that the benefits of processive enzyme-catalysed conversions of biomacromolecules can be leveraged to affect the selective hydrogenolysis of high-density polyethylene into a narrow distribution of diesel and lubricant-range alkanes using an ordered, mesoporous shell/active site/core catalyst architecture that incorporates catalytic platinum sites at the base of the mesopores. Solid-state nuclear magnetic resonance revealed that long hydrocarbon macromolecules readily move within the pores of this catalyst, with a subsequent escape being inhibited by polymer–surface interactions, a behaviour that resembles the binding and translocation of macromolecules in the catalytic cleft of processive enzymes. Accordingly, the hydrogenolysis of polyethylene with this catalyst proceeds processively to yield a reliable, narrow and tunable stream of alkane products.
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Data availability
Transmission electron microscopy, powder X-ray diffraction data and N2 sorption isotherms acquired to characterize inorganic materials, atomic coordinations from density functional theory calculations, NMR spectra and chromatography data that support the findings of this study are available in DataShare53 with the identifier https://doi.org/10.25380/iastate.12685775.
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Acknowledgements
This research is sponsored by the Catalysis for Polymer Upcycling, a project funded by the US Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Contract Numbers DE-AC-02-07CH11358 (Ames Laboratory) and DE-AC-02- 06CH11357 (Argonne National Laboratory). The authors thank the members of the Catalysis for Polymer Upcycling team, in particular S. Han, T. Keller, K. Poeppelmeier and R. Kennedy for numerous fruitful discussions.
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F.A.P. and A.L.P. conducted the SSNMR experiments under the direction of F.A.P., using *PE prepared and adsorbed onto mSiO2 by S.P. with guidance from G.W.C., A.M.L. and A.D.S. Silica materials and catalysts were prepared by X.W. and Y.P., under the direction of W.H. and I.I.S. A.T. performed the catalytic tests, under the direction of A.D.S. GPC experiments were performed by A.M.L. Product analysis was performed by A.T., R.A.H. and M.D. Signatures of processivity were proposed by B.P. Density functional theory calculations were performed by S.C.A. and A.H. F.A.P., W.H. and A.D.S. composed the manuscript with contributions from all the other co-authors.
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Supplementary methods, Tables 1–11 (N2 sorption, GPC data and GC data), discussion, Figs. (1–112) and references.
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XYZ coordinates of optimized DFT structures.
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Tennakoon, A., Wu, X., Paterson, A.L. et al. Catalytic upcycling of high-density polyethylene via a processive mechanism. Nat Catal 3, 893–901 (2020). https://doi.org/10.1038/s41929-020-00519-4
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DOI: https://doi.org/10.1038/s41929-020-00519-4
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