Polyethylene Terephthalate Deconstruction Catalyzed by a Carbon-Supported Single-Site Molybdenum-Dioxo Complex

Yosi Kratish; Jiaqi Li; Shanfu Liu; Yanshan Gao; Tobin J. Marks

doi:10.1002/anie.202007423

Polyethylene Terephthalate Deconstruction Catalyzed by a Carbon-Supported Single-Site Molybdenum-Dioxo Complex

Yosi Kratish, Jiaqi Li, Shanfu Liu, Yanshan Gao^*, Tobin J. Marks

^*Corresponding author for this work

Chemistry

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

1 Scopus citations

Abstract

Polyethylene terephthalate (PET) is selectively depolymerized by a carbon-supported single-site molybdenum-dioxo catalyst to terephthalic acid (PTA) and ethylene. The solventless reactions are most efficient under 1 atmosphere of H₂. The catalyst exhibits high stability and can be recycled multiple times without loss of activity. Waste beverage bottle PET or a PET + polypropylene (PP) mixture (simulating the bottle + cap) proceeds at 260 °C with complete PET deconstruction and quantitative PTA isolation. Mechanistic studies with a model diester, 1,2-ethanediol dibenzoate, suggest the reaction proceeds by initial retro-hydroalkoxylation/β-C−O scission and subsequent hydrogenolysis of the vinyl benzoate intermediate.

Original language	English (US)
Pages (from-to)	19857-19861
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	45
DOIs	https://doi.org/10.1002/anie.202007423
State	Published - Nov 2 2020

Keywords

heterogenous catalysis
hydrogenolysis
molybdenum
polymers
reaction mechanisms

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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title = "Polyethylene Terephthalate Deconstruction Catalyzed by a Carbon-Supported Single-Site Molybdenum-Dioxo Complex",

abstract = "Polyethylene terephthalate (PET) is selectively depolymerized by a carbon-supported single-site molybdenum-dioxo catalyst to terephthalic acid (PTA) and ethylene. The solventless reactions are most efficient under 1 atmosphere of H2. The catalyst exhibits high stability and can be recycled multiple times without loss of activity. Waste beverage bottle PET or a PET + polypropylene (PP) mixture (simulating the bottle + cap) proceeds at 260 °C with complete PET deconstruction and quantitative PTA isolation. Mechanistic studies with a model diester, 1,2-ethanediol dibenzoate, suggest the reaction proceeds by initial retro-hydroalkoxylation/β-C−O scission and subsequent hydrogenolysis of the vinyl benzoate intermediate.",

keywords = "heterogenous catalysis, hydrogenolysis, molybdenum, polymers, reaction mechanisms",

author = "Yosi Kratish and Jiaqi Li and Shanfu Liu and Yanshan Gao and Marks, {Tobin J.}",

note = "Funding Information: Financial support from the Office of Basic Energy Sciences, Department of Energy (DE-FG02-03ER15457) to the Institute for Catalysis in Energy Processes (ICEP) at Northwestern University (Y.K., J.L.) is gratefully acknowledged. Purchase of the NMR instrumentation at IMSERC was supported by NSF (CHE-1048773). We thank Katia Kratish for expert graphics design.",

year = "2020",

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doi = "10.1002/anie.202007423",

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AU - Kratish, Yosi

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AU - Gao, Yanshan

AU - Marks, Tobin J.

N1 - Funding Information: Financial support from the Office of Basic Energy Sciences, Department of Energy (DE-FG02-03ER15457) to the Institute for Catalysis in Energy Processes (ICEP) at Northwestern University (Y.K., J.L.) is gratefully acknowledged. Purchase of the NMR instrumentation at IMSERC was supported by NSF (CHE-1048773). We thank Katia Kratish for expert graphics design.

PY - 2020/11/2

Y1 - 2020/11/2

N2 - Polyethylene terephthalate (PET) is selectively depolymerized by a carbon-supported single-site molybdenum-dioxo catalyst to terephthalic acid (PTA) and ethylene. The solventless reactions are most efficient under 1 atmosphere of H2. The catalyst exhibits high stability and can be recycled multiple times without loss of activity. Waste beverage bottle PET or a PET + polypropylene (PP) mixture (simulating the bottle + cap) proceeds at 260 °C with complete PET deconstruction and quantitative PTA isolation. Mechanistic studies with a model diester, 1,2-ethanediol dibenzoate, suggest the reaction proceeds by initial retro-hydroalkoxylation/β-C−O scission and subsequent hydrogenolysis of the vinyl benzoate intermediate.

AB - Polyethylene terephthalate (PET) is selectively depolymerized by a carbon-supported single-site molybdenum-dioxo catalyst to terephthalic acid (PTA) and ethylene. The solventless reactions are most efficient under 1 atmosphere of H2. The catalyst exhibits high stability and can be recycled multiple times without loss of activity. Waste beverage bottle PET or a PET + polypropylene (PP) mixture (simulating the bottle + cap) proceeds at 260 °C with complete PET deconstruction and quantitative PTA isolation. Mechanistic studies with a model diester, 1,2-ethanediol dibenzoate, suggest the reaction proceeds by initial retro-hydroalkoxylation/β-C−O scission and subsequent hydrogenolysis of the vinyl benzoate intermediate.

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