Efficient Polyester Hydrogenolytic Deconstruction via Tandem Catalysis

Kratish, Yosi; Marks, Tobin J.

doi:10.1002/anie.202112576

Title: Efficient Polyester Hydrogenolytic Deconstruction via Tandem Catalysis

Journal Article · 15 December 2021 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202112576 · OSTI ID:1870850

Kratish, Yosi ^[1];

^[2]

Northwestern Univ., Evanston, IL (United States); Northwestern University
Northwestern Univ., Evanston, IL (United States)

Using a mechanism-based solvent-free tandem catalytic approach, commodity polyester plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) are rapidly and selectively deconstructed by combining the two air- and moisture-stable catalysts, Hf(OTf)₄ and Pd/C, under 1 atm H₂ , affording terephthalic acid (or naphthalene dicarboxylic acid for PEN) and ethane (or butane for PBT) in essentially quantitative yield. This process is effective for both laboratory grade and waste plastics, and comingled polypropylene remains unchanged. Combined experimental and DFT mechanistic analyses indicate that Hf(OTf)₄ catalyzes a mildly exergonic retro-hydroalkoxylation reaction in which an alkoxy C-O bond is first cleaved, yielding a carboxylic acid and alkene, and this process is closely coupled to an exergonic olefin hydrogenation step, driving the overall reaction forward.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-03ER15457

OSTI ID:: 1870850

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 9 Vol. 61; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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