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

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

doi:10.1038/s41467-024-49827-4

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

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

Research output: Contribution to journal › Article › peer-review

Abstract

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.

Original language	English
Article number	5785
Journal	Nature Communications
Volume	15
Issue number	1
DOIs	https://doi.org/10.1038/s41467-024-49827-4
State	Published - Dec 2024
Externally published	Yes

Funding

We thank Dr. Camelia N. Borca from the Phoenix beamline at the Swiss Light Source (SLS) of the Paul Scherrer Institute in Switzerland for their assistance in Al XAS characterization. We also thank G. L. Haller (Yale University), J. G. Chen (Columbia University), S. L. Scott (UC Santa Barbara), and M. L. Sarazen (Princeton University) for their discussion of the manuscript and helpful suggestions. J.A.L., W.Z., S.K., L. H., W.H., J.M., B.Y., O.Y.G., D.R., J.F., D.M.C., J.H., H.W., and M.L. thank the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences and Biosciences (towards a polyolefin-based refinery: understanding and controlling the critical reaction steps, FWP 78459) for funding support. J.H also thank the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences and Biosciences (Multifunctional Catalysis to Synthesize and Utilize Energy Carrier, FWP 47319) for funding support of in situ NMR work. Computational work was performed using the National Energy Research Scientific Computing Center located at the Lawrence Berkley National Laboratory provided by a user proposal and the Research Computing Facility at PNNL.

Funders	Funder number
Basic Energy Sciences
Pacific Northwest National Laboratory
National Energy Research Scientific Computing Center
U.S. Department of Energy
Yale University
Columbia University
Office of Science
University of California, Santa Barbara
Chemical Sciences, Geosciences, and Biosciences Division	FWP 47319, FWP 78459

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Zhang, W., Khare, R., Kim, S., Hale, L., Hu, W., Yuan, C., Sheng, Y., Zhang, P., Wahl, L., Mai, J., Yang, B., Gutiérrez, O. Y., Ray, D., Fulton, J., Camaioni, D. M., Hu, J., Wang, H., Lee, M. S., & Lercher, J. A. (2024). Active species in chloroaluminate ionic liquids catalyzing low-temperature polyolefin deconstruction. Nature Communications, 15(1), Article 5785. https://doi.org/10.1038/s41467-024-49827-4

@article{d20bd71f815d48668b1d339fea59bab8,

title = "Active species in chloroaluminate ionic liquids catalyzing low-temperature polyolefin deconstruction",

abstract = "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.",

author = "Wei Zhang and Rachit Khare and Sungmin Kim and Lillian Hale and Wenda Hu and Chunlin Yuan and Yaoci Sheng and Peiran Zhang and Lennart Wahl and Jiande Mai and Boda Yang and Guti{\'e}rrez, {Oliver Y.} and Debmalya Ray and John Fulton and Camaioni, {Donald M.} and Jianzhi Hu and Huamin Wang and Lee, {Mal Soon} and Lercher, {Johannes A.}",

note = "Publisher Copyright: {\textcopyright} Battelle Memorial Institute and The Authors 2024.",

year = "2024",

month = dec,

doi = "10.1038/s41467-024-49827-4",

language = "English",

volume = "15",

journal = "Nature Communications",

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Zhang, W, Khare, R, Kim, S, Hale, L, Hu, W, Yuan, C, Sheng, Y, Zhang, P, Wahl, L, Mai, J, Yang, B, Gutiérrez, OY, Ray, D, Fulton, J, Camaioni, DM, Hu, J, Wang, H, Lee, MS & Lercher, JA 2024, 'Active species in chloroaluminate ionic liquids catalyzing low-temperature polyolefin deconstruction', Nature Communications, vol. 15, no. 1, 5785. https://doi.org/10.1038/s41467-024-49827-4

TY - JOUR

T1 - Active species in chloroaluminate ionic liquids catalyzing low-temperature polyolefin deconstruction

AU - Zhang, Wei

AU - Khare, Rachit

AU - Kim, Sungmin

AU - Hale, Lillian

AU - Hu, Wenda

AU - Yuan, Chunlin

AU - Sheng, Yaoci

AU - Zhang, Peiran

AU - Wahl, Lennart

AU - Mai, Jiande

AU - Yang, Boda

AU - Gutiérrez, Oliver Y.

AU - Ray, Debmalya

AU - Fulton, John

AU - Camaioni, Donald M.

AU - Hu, Jianzhi

AU - Wang, Huamin

AU - Lee, Mal Soon

AU - Lercher, Johannes A.

PY - 2024/12

Y1 - 2024/12

N2 - 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.

AB - 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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DO - 10.1038/s41467-024-49827-4

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SN - 2041-1723

VL - 15

JO - Nature Communications

JF - Nature Communications

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ER -

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

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