Upcycling Single-Use Polyethylene into High-Quality Liquid Products

Gokhan Celik; Robert M. Kennedy; Ryan A. Hackler; Magali Ferrandon; Akalanka Tennakoon; Smita Patnaik; Anne M. Lapointe; Salai C. Ammal; Andreas Heyden; Frédéric A. Perras; Marek Pruski; Susannah L. Scott; Kenneth R. Poeppelmeier; Aaron D. Sadow; Massimiliano Delferro

doi:10.1021/acscentsci.9b00722

Upcycling Single-Use Polyethylene into High-Quality Liquid Products

Gokhan Celik, Robert M. Kennedy, Ryan A. Hackler, Magali Ferrandon, Akalanka Tennakoon, Smita Patnaik, Anne M. Lapointe, Salai C. Ammal, Andreas Heyden, Frédéric A. Perras, Marek Pruski, Susannah L. Scott, Kenneth R. Poeppelmeier^*, Aaron D. Sadow, Massimiliano Delferro

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

325 Scopus citations

Abstract

Our civilization relies on synthetic polymers for all aspects of modern life; yet, inefficient recycling and extremely slow environmental degradation of plastics are causing increasing concern about their widespread use. After a single use, many of these materials are currently treated as waste, underutilizing their inherent chemical and energy value. In this study, energy-rich polyethylene (PE) macromolecules are catalytically transformed into value-added products by hydrogenolysis using well-dispersed Pt nanoparticles (NPs) supported on SrTiO₃ perovskite nanocuboids by atomic layer deposition. Pt/SrTiO₃ completely converts PE (M_n = 8000-158,000 Da) or a single-use plastic bag (M_n = 31,000 Da) into high-quality liquid products, such as lubricants and waxes, characterized by a narrow distribution of oligomeric chains, at 170 psi H₂ and 300 °C under solvent-free conditions for reaction durations up to 96 h. The binding of PE onto the catalyst surface contributes to the number averaged molecular weight (M_n) and the narrow polydispersity (D) of the final liquid product. Solid-state nuclear magnetic resonance of ¹³C-enriched PE adsorption studies and density functional theory computations suggest that PE adsorption is more favorable on Pt sites than that on the SrTiO₃ support. Smaller Pt NPs with higher concentrations of undercoordinated Pt sites over-hydrogenolyzed PE to undesired light hydrocarbons.

Original language	English (US)
Pages (from-to)	1795-1803
Number of pages	9
Journal	ACS Central Science
Volume	5
Issue number	11
DOIs	https://doi.org/10.1021/acscentsci.9b00722
State	Published - Nov 27 2019

Funding

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscentsci.9b00722 . General procedures regarding synthesis, characterization, and activity experiments and supplemental data ( PDF ) Additional data ( ZIP ) XYZ coordinates of optimized structures ( PDF ) This work was supported as part of Catalysis for Polymer Upcycling (CPU) by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Contract DE-AC-02-06CH11357 (Argonne National Laboratory) and DE-AC-02 07CH11358 (Ames Laboratory). The authors declare the following competing financial interest(s): Two patent applications partially based on this work have been filed (US Patent Applications 62/796,482 and 62/892,347). The authors acknowledge Dr. D. M. Kaphan and Dr. J. Wen for helpful discussions. This work made use of the Center for Nanoscale Materials, an Office of Science user facility, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This work also made use of (i) the EPIC and BioCryo facilities of Northwestern University’s NU ANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN, (ii) CryoCluster equipment, which has received support from the MRI program (NSF DMR-1229693), and (iii) Jerome B. Cohen X-ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205). Finally, computational resources provided by XSEDE resources located at San Diego Supercomputer Center and Texas Advanced Computing Center (Grant No. TG-CTS090100) as well as Pacific Northwest National Laboratory (Ringgold ID 130367, Grant Proposal 50576) are gratefully acknowledged.

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering

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10.1021/acscentsci.9b00722

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Celik, G., Kennedy, R. M., Hackler, R. A., Ferrandon, M., Tennakoon, A., Patnaik, S., Lapointe, A. M., Ammal, S. C., Heyden, A., Perras, F. A., Pruski, M., Scott, S. L., Poeppelmeier, K. R., Sadow, A. D., & Delferro, M. (2019). Upcycling Single-Use Polyethylene into High-Quality Liquid Products. ACS Central Science, 5(11), 1795-1803. https://doi.org/10.1021/acscentsci.9b00722

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title = "Upcycling Single-Use Polyethylene into High-Quality Liquid Products",

abstract = "Our civilization relies on synthetic polymers for all aspects of modern life; yet, inefficient recycling and extremely slow environmental degradation of plastics are causing increasing concern about their widespread use. After a single use, many of these materials are currently treated as waste, underutilizing their inherent chemical and energy value. In this study, energy-rich polyethylene (PE) macromolecules are catalytically transformed into value-added products by hydrogenolysis using well-dispersed Pt nanoparticles (NPs) supported on SrTiO3 perovskite nanocuboids by atomic layer deposition. Pt/SrTiO3 completely converts PE (Mn = 8000-158,000 Da) or a single-use plastic bag (Mn = 31,000 Da) into high-quality liquid products, such as lubricants and waxes, characterized by a narrow distribution of oligomeric chains, at 170 psi H2 and 300 °C under solvent-free conditions for reaction durations up to 96 h. The binding of PE onto the catalyst surface contributes to the number averaged molecular weight (Mn) and the narrow polydispersity (D) of the final liquid product. Solid-state nuclear magnetic resonance of 13C-enriched PE adsorption studies and density functional theory computations suggest that PE adsorption is more favorable on Pt sites than that on the SrTiO3 support. Smaller Pt NPs with higher concentrations of undercoordinated Pt sites over-hydrogenolyzed PE to undesired light hydrocarbons.",

author = "Gokhan Celik and Kennedy, {Robert M.} and Hackler, {Ryan A.} and Magali Ferrandon and Akalanka Tennakoon and Smita Patnaik and Lapointe, {Anne M.} and Ammal, {Salai C.} and Andreas Heyden and Perras, {Fr{\'e}d{\'e}ric A.} and Marek Pruski and Scott, {Susannah L.} and Poeppelmeier, {Kenneth R.} and Sadow, {Aaron D.} and Massimiliano Delferro",

note = "Funding Information: The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscentsci.9b00722 . General procedures regarding synthesis, characterization, and activity experiments and supplemental data ( PDF ) Additional data ( ZIP ) XYZ coordinates of optimized structures ( PDF ) This work was supported as part of Catalysis for Polymer Upcycling (CPU) by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Contract DE-AC-02-06CH11357 (Argonne National Laboratory) and DE-AC-02 07CH11358 (Ames Laboratory). The authors declare the following competing financial interest(s): Two patent applications partially based on this work have been filed (US Patent Applications 62/796,482 and 62/892,347). Funding Information: The authors acknowledge Dr. D. M. Kaphan and Dr. J. Wen for helpful discussions. This work made use of the Center for Nanoscale Materials, an Office of Science user facility, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This work also made use of (i) the EPIC and BioCryo facilities of Northwestern University{\textquoteright}s NU ANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN, (ii) CryoCluster equipment, which has received support from the MRI program (NSF DMR-1229693), and (iii) Jerome B. Cohen X-ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205). Finally, computational resources provided by XSEDE resources located at San Diego Supercomputer Center and Texas Advanced Computing Center (Grant No. TG-CTS090100) as well as Pacific Northwest National Laboratory (Ringgold ID 130367, Grant Proposal 50576) are gratefully acknowledged. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = nov,

day = "27",

doi = "10.1021/acscentsci.9b00722",

language = "English (US)",

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AU - Celik, Gokhan

AU - Kennedy, Robert M.

AU - Hackler, Ryan A.

AU - Ferrandon, Magali

AU - Tennakoon, Akalanka

AU - Patnaik, Smita

AU - Lapointe, Anne M.

AU - Ammal, Salai C.

AU - Heyden, Andreas

AU - Perras, Frédéric A.

AU - Pruski, Marek

AU - Scott, Susannah L.

AU - Poeppelmeier, Kenneth R.

AU - Sadow, Aaron D.

AU - Delferro, Massimiliano

N1 - Funding Information: The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscentsci.9b00722 . General procedures regarding synthesis, characterization, and activity experiments and supplemental data ( PDF ) Additional data ( ZIP ) XYZ coordinates of optimized structures ( PDF ) This work was supported as part of Catalysis for Polymer Upcycling (CPU) by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Contract DE-AC-02-06CH11357 (Argonne National Laboratory) and DE-AC-02 07CH11358 (Ames Laboratory). The authors declare the following competing financial interest(s): Two patent applications partially based on this work have been filed (US Patent Applications 62/796,482 and 62/892,347). Funding Information: The authors acknowledge Dr. D. M. Kaphan and Dr. J. Wen for helpful discussions. This work made use of the Center for Nanoscale Materials, an Office of Science user facility, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This work also made use of (i) the EPIC and BioCryo facilities of Northwestern University’s NU ANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN, (ii) CryoCluster equipment, which has received support from the MRI program (NSF DMR-1229693), and (iii) Jerome B. Cohen X-ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205). Finally, computational resources provided by XSEDE resources located at San Diego Supercomputer Center and Texas Advanced Computing Center (Grant No. TG-CTS090100) as well as Pacific Northwest National Laboratory (Ringgold ID 130367, Grant Proposal 50576) are gratefully acknowledged. Publisher Copyright: © 2019 American Chemical Society.

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N2 - Our civilization relies on synthetic polymers for all aspects of modern life; yet, inefficient recycling and extremely slow environmental degradation of plastics are causing increasing concern about their widespread use. After a single use, many of these materials are currently treated as waste, underutilizing their inherent chemical and energy value. In this study, energy-rich polyethylene (PE) macromolecules are catalytically transformed into value-added products by hydrogenolysis using well-dispersed Pt nanoparticles (NPs) supported on SrTiO3 perovskite nanocuboids by atomic layer deposition. Pt/SrTiO3 completely converts PE (Mn = 8000-158,000 Da) or a single-use plastic bag (Mn = 31,000 Da) into high-quality liquid products, such as lubricants and waxes, characterized by a narrow distribution of oligomeric chains, at 170 psi H2 and 300 °C under solvent-free conditions for reaction durations up to 96 h. The binding of PE onto the catalyst surface contributes to the number averaged molecular weight (Mn) and the narrow polydispersity (D) of the final liquid product. Solid-state nuclear magnetic resonance of 13C-enriched PE adsorption studies and density functional theory computations suggest that PE adsorption is more favorable on Pt sites than that on the SrTiO3 support. Smaller Pt NPs with higher concentrations of undercoordinated Pt sites over-hydrogenolyzed PE to undesired light hydrocarbons.

AB - Our civilization relies on synthetic polymers for all aspects of modern life; yet, inefficient recycling and extremely slow environmental degradation of plastics are causing increasing concern about their widespread use. After a single use, many of these materials are currently treated as waste, underutilizing their inherent chemical and energy value. In this study, energy-rich polyethylene (PE) macromolecules are catalytically transformed into value-added products by hydrogenolysis using well-dispersed Pt nanoparticles (NPs) supported on SrTiO3 perovskite nanocuboids by atomic layer deposition. Pt/SrTiO3 completely converts PE (Mn = 8000-158,000 Da) or a single-use plastic bag (Mn = 31,000 Da) into high-quality liquid products, such as lubricants and waxes, characterized by a narrow distribution of oligomeric chains, at 170 psi H2 and 300 °C under solvent-free conditions for reaction durations up to 96 h. The binding of PE onto the catalyst surface contributes to the number averaged molecular weight (Mn) and the narrow polydispersity (D) of the final liquid product. Solid-state nuclear magnetic resonance of 13C-enriched PE adsorption studies and density functional theory computations suggest that PE adsorption is more favorable on Pt sites than that on the SrTiO3 support. Smaller Pt NPs with higher concentrations of undercoordinated Pt sites over-hydrogenolyzed PE to undesired light hydrocarbons.

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Upcycling Single-Use Polyethylene into High-Quality Liquid Products

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