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

Lai, Qingheng; Zhang, Xinrui; Jiang, Shan; Krzyaniak, Matthew D.; Alayoglu, Selim; Agarwal, Amol; Liu, Yukun; Edenfield, Wilson C.; Kobayashi, Takeshi; Wang, Yuyang; Dravid, Vinayak; Wasielewski, Michael R.; Miller, Jeffery T.; Kratish, Yosi; Marks, Tobin J.

doi:10.1038/s41557-025-01892-y

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

Journal Article · Tue Sep 02 00:00:00 EDT 2025 · Nature Chemistry

DOI:https://doi.org/10.1038/s41557-025-01892-y· OSTI ID:2998113

^[1]; Zhang, Xinrui ^[1]; Jiang, Shan ^[2]; ^[1]; Alayoglu, Selim ^[1]; Agarwal, Amol ^[1]; Liu, Yukun ^[1]; Edenfield, Wilson C. ^[1]; ^[3]; Wang, Yuyang ^[1]; ^[1]; ^[1]; ^[2]; ^[1]; ^[1]

Northwestern Univ., Evanston, IL (United States)
Purdue Univ., West Lafayette, IN (United States)
Ames Laboratory (AMES), Ames, IA (United States); Iowa State Univ., Ames, IA (United States)

Current methods of processing accumulated polyolefin waste typically require harsh conditions, precious metals or high metal loadings to achieve appreciable activities. Here, in this work, 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/Ni^IIH 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/Ni^IIH 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.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States); Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-07CH11358; FG02-99ER14999; SC0001329; SC0012704; SC0024448

OSTI ID:: 2998113

Alternate ID(s):: OSTI ID: 3014155

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 10 Vol. 17; ISSN 1755-4349; ISSN 1755-4330

Publisher:: Springer Science and Business Media LLCCopyright Statement

Country of Publication:: United States

Language:: English

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