Rapid atom-efficient polyolefin plastics hydrogenolysis mediated by a well-defined single-site electrophilic/cationic organo-zirconium catalyst

Alexander H. Mason, Alessandro Motta, Anusheela Das, Qing Ma, Michael J. Bedzyk*, Yosi Kratish*, Tobin J. Marks*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

42 Scopus citations

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 H2 with 0.02 mol% catalyst loading. For polyethylene, quantitative hydrogenolysis to light hydrocarbons proceeds within 48 min with an activity of > 4000 mol(CH2 units)·mol(Zr)−1·h−1 at 200 °C/2 atm H2 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.

Original languageEnglish (US)
Article number7187
JournalNature communications
Volume13
Issue number1
DOIs
StatePublished - Dec 2022

Funding

Financial support was provided by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DOE DE-FG02-03ER15457 (T.J.M.) to the Institute for Catalysis in Energy Processes (ICEP) at Northwestern University (NU). This work made use of IMSERC facilities at NU, which has received support from Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), International Institute of Nanotechnology (IIN), and NU. This work made use of the NU QBIC supported by NASA Ames Research Center Grant NNA04CC36G. This work made use of the REACT Facility of NU’s Center for Catalysis and Surface Science supported by a grant from the DOE (DE-SC0001329). This work used the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) 5BM-D beamline at the Advanced Photon Source (APS). DND-CAT is supported by NU, E.I. DuPont de Nemours & Co., and The Dow Chemical Company. A.P.S. is supported by DOE at Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This research was supported in part by the computational resources and staff contributions provided by the Quest High-Performance Computing Facility at NU, which is jointly supported by the Office of the Provost, the Office for Research, and NU Information Technology. Computational support was also provided by the CINECA HPC center under the ISCRA initiative (award no. HP10CC5WSY 2020). We thank Dr. J. Li for insightful discussions of reaction kinetics and Dr. R. Pankow for his diligent effort in repairing, maintaining, and training students on the GPC. Financial support was provided by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DOE DE-FG02-03ER15457 (T.J.M.) to the Institute for Catalysis in Energy Processes (ICEP) at Northwestern University (NU). This work made use of IMSERC facilities at NU, which has received support from Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), International Institute of Nanotechnology (IIN), and NU. This work made use of the NU QBIC supported by NASA Ames Research Center Grant NNA04CC36G. This work made use of the REACT Facility of NU’s Center for Catalysis and Surface Science supported by a grant from the DOE (DE-SC0001329). This work used the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) 5BM-D beamline at the Advanced Photon Source (APS). DND-CAT is supported by NU, E.I. DuPont de Nemours & Co., and The Dow Chemical Company. A.P.S. is supported by DOE at Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This research was supported in part by the computational resources and staff contributions provided by the Quest High-Performance Computing Facility at NU, which is jointly supported by the Office of the Provost, the Office for Research, and NU Information Technology. Computational support was also provided by the CINECA HPC center under the ISCRA initiative (award no. HP10CC5WSY 2020). We thank Dr. J. Li for insightful discussions of reaction kinetics and Dr. R. Pankow for his diligent effort in repairing, maintaining, and training students on the GPC.

ASJC Scopus subject areas

  • General Chemistry
  • General Biochemistry, Genetics and Molecular Biology
  • General Physics and Astronomy

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