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Stable single-site organonickel catalyst preferentially hydrogenolyses branched polyolefin C–C bonds

Nature Chemistry volume 17, pages 1488–1496 (2025)Cite this article

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Abstract

Current methods of processing accumulated polyolefin waste typically require harsh conditions, precious metals or high metal loadings to achieve appreciable activities. Here we examined supported, single-site organonickel catalysts for polyolefin upcycling. Chemisorption of Ni(COD)2 (COD, 1,5-cyclooctadiene) onto Brønsted acidic sulfated alumina (AlS) yields a highly electrophilic Ni(I) precatalyst, AlS/Ni(COD)2, which is converted under H2 to the active AlS/NiIIH catalyst. This single-site system exhibits unique hydrogenolysis selectivity that favours cleaving branched polyolefin C–C linkages, enabling the hydrogenolytic separation of polyethylene and isotactic polypropylene (iPP) mixtures. Moreover, AlS/NiIIH remains highly selective and active for hydrogenolysis of iPP admixed with polyvinyl chloride, and the spent catalyst can be repeatedly regenerated by AlEt3 treatment. Experimental mechanistic analysis and density functional theory modelling reveal a turnover-limiting C–C scission pathway featuring β-alkyl transfer and strong olefin binding. These results highlight the potential of nickel-based systems for the selective upcycling of complex plastic waste streams.

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Fig. 1: Precatalyst chemisorption pathways.
Fig. 2: DRIFTS, XPS and DFT analysis.
Fig. 3: DFT analysis of propane hydrogenolysis catalysed by AlS/NiH.
Fig. 4: Hydrogenolysis with recycled catalyst.

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Data availability

All relevant data supporting the findings of this study are available in this paper and its Supplementary Information. Synthetic procedures and characterization for the catalysts, computational studies and all copies of NMR, XPS spectra and GPC traces are available in the Supplementary Information. Source data are provided with this paper.

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Acknowledgements

We thank the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under award number DOE DE-SC0024448, and The Dow Chemical Company for financial support of this work (T.J.M., Q.L., W.C.E., A.A., catalyst synthesis and characterization). X.Z. thanks the Center for Innovative and Strategic Transformation of Alkane Resources (CISTAR) for support under NSF award number EEC-1647722 (XPS). A part of this work (T.K., solid-state NMR) was supported by the US DOE, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. The research was performed at the Ames National Laboratory, which is operated for the US DOE by Iowa State University under contract number DE-AC02-07CH11358. This work made use of IMSERC (RRID SCR_017874) facilities at Northwestern University, which received support from Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSFECCS-2025633), the International Institute of Nanotechnology and Northwestern University. This work made use of the Northwestern University QBIC supported by NASA Ames Research Center grant NNA04CC36G. This work made use of the REACT Facility of Northwestern University’s Center for Catalysis and Surface Science supported by grant DE-SC0001329 from the DOE. This work was supported by the US DOE, Office of Science, Office of Basic Energy Sciences, under award number DE-FG02-99ER14999 (M.R.W., EPR spectroscopy). This research used resources at the 8-ID beamline of the National Synchrotron Light Source II, a US DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract number DE-SC0012704. This research was supported in part by computational resources and staff 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. We also thank B. Tumanskii for informative and helpful discussions.

Author information

Authors and Affiliations

  1. Department of Chemistry and the Trienens Institute for Sustainability and Energy, Northwestern University, Evanston, IL, USA

    Qingheng Lai, Matthew D. Krzyaniak, Wilson C. Edenfield, Yuyang Wang, Michael R. Wasielewski, Yosi Kratish & Tobin J. Marks

  2. Department of Materials Science & Engineering, Northwestern University, Evanston, IL, USA

    Xinrui Zhang, Amol Agarwal, Yukun Liu & Vinayak Dravid

  3. Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN, USA

    Shan Jiang & Jeffery T. Miller

  4. Center for Catalysis and Surface Science, Northwestern University, Evanston, IL, USA

    Selim Alayoglu

  5. US DOE Ames National Laboratory, Iowa State University, Ames, Iowa, USA

    Takeshi Kobayashi

Authors
  1. Qingheng Lai
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  3. Shan Jiang
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Contributions

Q.L., Y.K. and T.J.M. designed the study. Q.L., Y.K. and T.J.M. wrote the paper with contributions from all coauthors. Q.L. performed the catalyst preparation, characterization and catalytic tests. Y.K. carried out the theoretical calculations. X.Z. performed XPS measurements and analysis. S.J. and J.T.M. performed XAS measurement and analysis. M.D.K. performed EPR measurements and analysis. Y.L. performed the HAADF-STEM measurements. S.A. performed the DRIFTS measurements and analysis. T.K. performed the solid-state NMR experiments and analysis. X.Z. helped to set up the continuous-flow BenchCat reactor. Q.L., X.Z., S.J., M.D.K., S.A., A.A., M.R.W., V.D., Y.W., W.C.E., J.T.M., Y.K. and T.J.M. analysed the data and revised the paper.

Corresponding authors

Correspondence to Jeffery T. Miller, Yosi Kratish or Tobin J. Marks.

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Extended data

Extended Data Fig. 1 potential cleaving point in PECO and analysis of DCM extract from hydrogenolysis of polyolefins or polyolefin mixtures.

a, GC–MS chromatogram of the DCM extract of PECO hydrogenolysis reactions run under identical conditions with the indicated catalysts; b, Potential C-C cleavage points in PECO hydrogenolysis. c, GPC analysis of the DCM extract of i-PP hydrogenolysis. d, GPC analysis of the DCM extract of a-PP hydrogenolysis. e, GPC analysis of DCM extract of hydrogenolysis of post-consumer i-PP and PE mixtures. f, GPC analysis of the solid fraction of hydrogenolysis of post-consumer i-PP and PE mixtures.

Source data

Extended Data Fig. 2 GPC analysis of DCM extract of i-PP hydrogenolysis in the presence of PVC.

a, GPC analysis of DCM extract of i-PP hydrogenolysis in the presence of PVC with constant total polymer mass (~500 mg). b, GPC analysis of DCM extract of i-PP hydrogenolysis in the presence of varied PVC content (~500 mg i-PP loading).

Source data

Extended Data Fig. 3 GPC analysis of DCM extract of i-PP hydrogenolysis under other conditions.

a, GPC analysis of DCM extract of i-PP hydrogenolysis in the presence of 10% PTFE. b, GPC analysis of DCM extract of i-PP hydrogenolysis with PVC pretreated AlS/Ni(COD)2.

Source data

Extended Data Table 1 AlS/Ni(COD)2 (1)-mediated stepwise hydrogenolysis data for mixtures of post-consumer i-PP and linear PE polymer
Full size table
Extended Data Table 2 Catalytic AlS/Ni(COD)2 (1) i-PP hydrogenolysis data in the presence of PVC
Full size table
Extended Data Table 3 AlS/Ni(COD)2 (1)-mediated i-PP hydrogenolysis data under various conditions
Full size table

Supplementary information

Supplementary Information

Supplementary procedures, physical methods, Figs. 1–36 and Tables 1–13.

Supplementary Data 1

DFT model construction and Cartesian coordinates.

Source data

Source Data Fig. 2

Statistical source data.

Source Data Fig. 3

Computed energy values.

Source Data Fig. 4

Statistical source data.

Source Data Extended Data Fig. 1

Statistical source data.

Source Data Extended Data Fig. 2

Statistical source data.

Source Data Extended Data Fig. 3

Statistical source data.

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Lai, Q., Zhang, X., Jiang, S. et al. Stable single-site organonickel catalyst preferentially hydrogenolyses branched polyolefin C–C bonds. Nat. Chem. 17, 1488–1496 (2025). https://doi.org/10.1038/s41557-025-01892-y

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