Active species in chloroaluminate ionic liquids catalyzing low-temperature polyolefin deconstruction

Zhang, Wei; Khare, Rachit; Kim, Sungmin; Hale, Lillian; Hu, Wenda; Yuan, Chunlin; Sheng, Yaoci; Zhang, Peiran; Wahl, Lennart; Mai, Jiande; Yang, Boda; Gutiérrez, Oliver Y.; Ray, Debmalya; Fulton, John; Camaioni, Donald M.; Hu, Jianzhi; Wang, Huamin; Lee, Mal-Soon; Lercher, Johannes A.

doi:10.1038/s41467-024-49827-4

Active species in chloroaluminate ionic liquids catalyzing low-temperature polyolefin deconstruction

Journal Article · Wed Jul 10 00:00:00 EDT 2024 · Nature Communications

DOI:https://doi.org/10.1038/s41467-024-49827-4· OSTI ID:2396801

^[1]; Khare, Rachit ^[2]; ^[3]; Hale, Lillian ^[3]; Hu, Wenda ^[3]; Yuan, Chunlin ^[2]; Sheng, Yaoci ^[2]; ^[2]; Wahl, Lennart ^[2]; Mai, Jiande ^[3]; Yang, Boda ^[3]; ^[3]; Ray, Debmalya ^[3]; Fulton, John ^[3]; ^[3]; ^[4]; Wang, Huamin ^[3]; ^[3]; ^[1]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Technische Univ. München, Garching (Germany)
Technische Univ. München, Garching (Germany)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)

Chloroaluminate ionic liquids selectively transform (waste) polyolefins into gasoline-range alkanes through tandem cracking-alkylation at temperatures below 100 °C. Further improvement of this process necessitates a deep understanding of the nature of the catalytically active species and the correlated performance in the catalyzing critical reactions for the tandem polyolefin deconstruction with isoalkanes at low temperatures. Here, we address this requirement by determining the nuclearity of the chloroaluminate ions and their interactions with reaction intermediates, combining in situ ²⁷Al magic-angle spinning nuclear magnetic resonance spectroscopy, in situ Raman spectroscopy, Al K-edge X-ray absorption near edge structure spectroscopy, and catalytic activity measurement. Cracking and alkylation are facilitated by carbenium ions initiated by AlCl₃-tert-butyl chloride (TBC) adducts, which are formed by the dissociation of Al₂Cl₇^- in the presence of TBC. The carbenium ions activate the alkane polymer strands and advance the alkylation cycle through multiple hydride transfer reactions. In situ ¹H NMR and operando infrared spectroscopy demonstrate that the cracking and alkylation processes occur synchronously; alkenes formed during cracking are rapidly incorporated into the carbenium ion-mediated alkylation cycle. The conclusions are further supported by ab initio molecular dynamics simulations coupled with an enhanced sampling method, and model experiments using n-hexadecane as a feed.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

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

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2396801

Alternate ID(s):: OSTI ID: 2478149

Report Number(s):: PNNL-SA--184956

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 15; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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