Rapid Polyolefin Plastic Hydrogenolysis Mediated by Single-Site Heterogeneous Electrophilic/Cationic Organo-group IV Catalysts

Edenfield, Wilson C.; Mason, Alexander H.; Lai, Qingheng; Agarwal, Amol; Kobayashi, Takeshi; Kratish, Yosi; Marks, Tobin J.

doi:10.1021/acscatal.3c05161

Title: Rapid Polyolefin Plastic Hydrogenolysis Mediated by Single-Site Heterogeneous Electrophilic/Cationic Organo-group IV Catalysts

Journal Article · 26 December 2023 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.3c05161 · OSTI ID:2281347

Edenfield, Wilson C. ^[1]; Mason, Alexander H. ^[1]; Lai, Qingheng ^[1]; Agarwal, Amol ^[1];

^[2];

^[1];

^[1]

Northwestern Univ., Evanston, IL (United States)
Ames Laboratory (AMES), Ames, IA (United States)

A homologous series of cationic electrophilic group IV metal hydrides (M = Ti, Zr, Hf) created by chemisorption of the corresponding MNp₄ precursors on highly Brønsted acidic sulfated alumina (AlS) to yield loosely coordinated surface AlS/MNp₂ (Np = neopentyl) species are systematically characterized by ICP, EXAFS/XANES, DRIFTS, and solid-state high-resolution multidimensional NMR spectroscopy (SSNMR), as well as by energy span DFT computation. With effective stirring, these complexes readily undergo reaction with H₂ to yield AlS/M(alkyl)H species, which are highly active for the hydrogenolysis of diverse commercial polyethylenes, α-olefin-ethylene copolymers, isotactic polypropylene, and postconsumer polyolefins including high-density polyethylenes, yielding medium and small linear and branched hydrocarbons at turnover frequencies as high as 36,300 h^–1 at 200 °C/17 atm H₂ for M = Zr. For given polyolefin and reaction conditions, turnover frequencies scale approximately as M = Zr > Hf > Ti, whereas catalyst thermal stability scales approximately as M = Hf ≈ Zr > Ti, and these trends are qualitatively understandable from the DFT analysis. These catalytic results reveal that the AlS/Hf(R)H-mediated hydrogenolysis favors wax-like and liquid products, whereas the AlS/Zr(R)H-mediated hydrogenolysis can be tuned between gases and liquids. Finally, DFT analysis identifies β-alkyl elimination as the turnover-limiting C–C scission process, which is particularly facile in these cationic d⁰ complexes but not so in the neutrally charged analogues.

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Research Organization:: Ames Laboratory (AMES), Ames, IA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: AC02-06CH11357; FG02-03ER15457; SC0014664; SC0001329; AC02-07CH11358; SC0024448

OSTI ID:: 2281347

Report Number(s):: IS-J-11,239

Journal Information:: ACS Catalysis, Vol. 14, Issue 1; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
polyolefin waste
chemical recycling
sulfated alumina
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zirconium
hydrogenolysis

Title: Rapid Polyolefin Plastic Hydrogenolysis Mediated by Single-Site Heterogeneous Electrophilic/Cationic Organo-group IV Catalysts

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