Rapid atom-efficient polyolefin plastics hydrogenolysis mediated by a well-defined single-site electrophilic/cationic organo-zirconium catalyst
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Abstract
Polyolefins comprise a major fraction of single-use plastics, yet their catalytic deconstruction/recycling has proven challenging due to their inert saturated hydrocarbon connectivities. Here a very electrophilic, formally cationic earth-abundant single-site organozirconium catalyst chemisorbed on a highly Brønsted acidic sulfated alumina support and characterized by a broad array of experimental and theoretical techniques, is shown to mediate the rapid hydrogenolytic cleavage of molecular and macromolecular saturated hydrocarbons under mild conditions, with catalytic onset as low as 90 °C/0.5 atm H 2 with 0.02 mol% catalyst loading. For polyethylene, quantitative hydrogenolysis to light hydrocarbons proceeds within 48 min with an activity of > 4000 mol(CH 2 units)·mol(Zr) −1 ·h −1 at 200 °C/2 atm H 2 pressure. Under similar solventless conditions, polyethylene- co −1-octene, isotactic polypropylene, and a post-consumer food container cap are rapidly hydrogenolyzed to low molecular mass hydrocarbons. Regarding mechanism, theory and experiment identify a turnover-limiting C-C scission pathway involving ß -alkyl transfer rather than the more common σ-bond metathesis.
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- Authors
- Mason, A. H., Motta, A., Das, A., Ma, Q., Bedzyk, M. J., Kratish, Y., & Marks, T. J.
- Affiliations
- Northwestern University (US)
- Sapienza University of Rome (IT)
- Corresponding author
- Bedzyk, Michael J.
- Kratish, Yosi
- Marks, Tobin J.
- ORCID
- Venue
- Nature Communications
- Published
- 2022-11-23
- Volume
- 13
- Issue
- 1
- Pages
- 7187-7187
- ISSN
- 2041-1723 (ISSN-L)
- PMC
- PMC9684440
- OpenAlex
- W4309883025
- Cited by
- 82
- References
- 47
- Citations by year
- 2026: 20 · 2025: 17 · 2024: 26 · 2023: 17 · 2022: 2
- FWCI
- 5.90
- Type
- journal article
- Language
- en
- Open access
- gold
- doi.org
- Locations
- Nature Communications (publishedVersion, cc-by)
- ChemRxiv (acceptedVersion, cc-by-nc-nd)
- PubMed Central (publishedVersion, cc-by)
- PubMed (publishedVersion)
- IRIS Research product catalog (Sapienza University of Rome) (submittedVersion, cc-by)
- RePEc: Research Papers in Economics (submittedVersion)
- DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
- OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
- Funders
- National Science Foundation (ECCS-2025633)
- DOE | LDRD | Argonne National Laboratory (DE-AC02-06CH11357)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Keywords
- polyolefin recycling, hydrogenolysis, polyethylene, polypropylene, post-consumer plastic waste, C–C bond cleavage, sigma-bond metathesis, atom economy, solvent-free catalysis, light hydrocarbons
- MeSH terms
- Cations, Hydrocarbons, Plastics, Polyenes, Polyethylenes, Zirconium
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