Bifunctional tandem catalytic upcycling of polyethylene to surfactant-range alkylaromatics

Jiakai Sun; Yu Hsuan Lee; Ryan D. Yappert; Anne M. LaPointe; Geoffrey W. Coates; Baron Peters; Mahdi M. Abu-Omar; Susannah L. Scott

doi:10.1016/j.chempr.2023.05.017

Bifunctional tandem catalytic upcycling of polyethylene to surfactant-range alkylaromatics

Jiakai Sun, Yu Hsuan Lee, Ryan D. Yappert, Anne M. LaPointe, Geoffrey W. Coates, Baron Peters, Mahdi M. Abu-Omar, Susannah L. Scott

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

Abstract

Catalytic conversion of waste polyolefins to value-added alkylaromatics could contribute to carbon recycling. Compared with tandem hydrogenolysis/aromatization of polyethylene (PE) catalyzed by Pt/γ-Al₂O₃ at 280°C, both a 5-fold enhancement in the rate of C–C bond scission and a doubling of the molar yield of alkylaromatics were achieved using a more acidic Pt/F-Al₂O₃ catalyst instead. Bifunctional (metal/acid) catalysts also generate alkylaromatic products with lower average carbon numbers (ca. C₂₀), similar to conventional anionic surfactants. Because physical mixtures of weakly acidic Pt/γ-Al₂O₃ or non-acidic Pt/SiO₂ with strongly Brønsted acidic Cl-Al₂O₃ or F-Al₂O₃ are also effective, the tandem reaction does not require nanoscale intimacy between metal and acid active sites. Kinetic studies using triacontane (norm-C₃₀H₆₂) as a model for PE show that the Pt-catalyzed dehydrogenation/hydrogenation reactions are quasi-equilibrated, while the acid-catalyzed C–C bond scission and skeletal transformations (isomerization and cyclization) determine the overall rates of depolymerization and aromatic formation.

Original language	English (US)
Pages (from-to)	2318-2336
Number of pages	19
Journal	Chem
Volume	9
Issue number	8
DOIs	https://doi.org/10.1016/j.chempr.2023.05.017
State	Published - Aug 10 2023

Keywords

SDG11: Sustainable cities and communities
SDG12: Responsible consumption and production
SDG9: Industry, innovation, and infrastructure
aromatization
bifunctional catalyst
depolymerization
nanoscale reaction coupling
plastic waste
polyethylene upcycling
tandem reaction

ASJC Scopus subject areas

General Chemistry
Biochemistry
Environmental Chemistry
General Chemical Engineering
Biochemistry, medical
Materials Chemistry

Online availability

10.1016/j.chempr.2023.05.017

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title = "Bifunctional tandem catalytic upcycling of polyethylene to surfactant-range alkylaromatics",

abstract = "Catalytic conversion of waste polyolefins to value-added alkylaromatics could contribute to carbon recycling. Compared with tandem hydrogenolysis/aromatization of polyethylene (PE) catalyzed by Pt/γ-Al2O3 at 280°C, both a 5-fold enhancement in the rate of C–C bond scission and a doubling of the molar yield of alkylaromatics were achieved using a more acidic Pt/F-Al2O3 catalyst instead. Bifunctional (metal/acid) catalysts also generate alkylaromatic products with lower average carbon numbers (ca. C20), similar to conventional anionic surfactants. Because physical mixtures of weakly acidic Pt/γ-Al2O3 or non-acidic Pt/SiO2 with strongly Br{\o}nsted acidic Cl-Al2O3 or F-Al2O3 are also effective, the tandem reaction does not require nanoscale intimacy between metal and acid active sites. Kinetic studies using triacontane (norm-C30H62) as a model for PE show that the Pt-catalyzed dehydrogenation/hydrogenation reactions are quasi-equilibrated, while the acid-catalyzed C–C bond scission and skeletal transformations (isomerization and cyclization) determine the overall rates of depolymerization and aromatic formation.",

keywords = "SDG11: Sustainable cities and communities, SDG12: Responsible consumption and production, SDG9: Industry, innovation, and infrastructure, aromatization, bifunctional catalyst, depolymerization, nanoscale reaction coupling, plastic waste, polyethylene upcycling, tandem reaction",

author = "Jiakai Sun and Lee, {Yu Hsuan} and Yappert, {Ryan D.} and LaPointe, {Anne M.} and Coates, {Geoffrey W.} and Baron Peters and Abu-Omar, {Mahdi M.} and Scott, {Susannah L.}",

note = "This work was supported by a subcontract from the Ames Laboratory with funding from the U.S. Department of Energy , Office of Science , Office of Basic Energy Sciences , under contract no. DE-AC02-07CH11358 as part of the Energy Frontier Research Center entitled the Institute for Cooperative Upcycling of Plastics (iCOUP). Some experiments were performed using UC Santa Barbara{\textquoteright}s MRL Shared Experimental Facilities, supported by the MRSEC Program of the NSF under award DMR 1720256 , a member of the NSF-funded Materials Research Facilities Network ( www.mrfn.org ).",

year = "2023",

month = aug,

day = "10",

doi = "10.1016/j.chempr.2023.05.017",

language = "English (US)",

volume = "9",

pages = "2318--2336",

journal = "Chem",

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T1 - Bifunctional tandem catalytic upcycling of polyethylene to surfactant-range alkylaromatics

AU - Sun, Jiakai

AU - Lee, Yu Hsuan

AU - Yappert, Ryan D.

AU - LaPointe, Anne M.

AU - Coates, Geoffrey W.

AU - Peters, Baron

AU - Abu-Omar, Mahdi M.

AU - Scott, Susannah L.

N1 - This work was supported by a subcontract from the Ames Laboratory with funding from the U.S. Department of Energy , Office of Science , Office of Basic Energy Sciences , under contract no. DE-AC02-07CH11358 as part of the Energy Frontier Research Center entitled the Institute for Cooperative Upcycling of Plastics (iCOUP). Some experiments were performed using UC Santa Barbara’s MRL Shared Experimental Facilities, supported by the MRSEC Program of the NSF under award DMR 1720256 , a member of the NSF-funded Materials Research Facilities Network ( www.mrfn.org ).

PY - 2023/8/10

Y1 - 2023/8/10

N2 - Catalytic conversion of waste polyolefins to value-added alkylaromatics could contribute to carbon recycling. Compared with tandem hydrogenolysis/aromatization of polyethylene (PE) catalyzed by Pt/γ-Al2O3 at 280°C, both a 5-fold enhancement in the rate of C–C bond scission and a doubling of the molar yield of alkylaromatics were achieved using a more acidic Pt/F-Al2O3 catalyst instead. Bifunctional (metal/acid) catalysts also generate alkylaromatic products with lower average carbon numbers (ca. C20), similar to conventional anionic surfactants. Because physical mixtures of weakly acidic Pt/γ-Al2O3 or non-acidic Pt/SiO2 with strongly Brønsted acidic Cl-Al2O3 or F-Al2O3 are also effective, the tandem reaction does not require nanoscale intimacy between metal and acid active sites. Kinetic studies using triacontane (norm-C30H62) as a model for PE show that the Pt-catalyzed dehydrogenation/hydrogenation reactions are quasi-equilibrated, while the acid-catalyzed C–C bond scission and skeletal transformations (isomerization and cyclization) determine the overall rates of depolymerization and aromatic formation.

AB - Catalytic conversion of waste polyolefins to value-added alkylaromatics could contribute to carbon recycling. Compared with tandem hydrogenolysis/aromatization of polyethylene (PE) catalyzed by Pt/γ-Al2O3 at 280°C, both a 5-fold enhancement in the rate of C–C bond scission and a doubling of the molar yield of alkylaromatics were achieved using a more acidic Pt/F-Al2O3 catalyst instead. Bifunctional (metal/acid) catalysts also generate alkylaromatic products with lower average carbon numbers (ca. C20), similar to conventional anionic surfactants. Because physical mixtures of weakly acidic Pt/γ-Al2O3 or non-acidic Pt/SiO2 with strongly Brønsted acidic Cl-Al2O3 or F-Al2O3 are also effective, the tandem reaction does not require nanoscale intimacy between metal and acid active sites. Kinetic studies using triacontane (norm-C30H62) as a model for PE show that the Pt-catalyzed dehydrogenation/hydrogenation reactions are quasi-equilibrated, while the acid-catalyzed C–C bond scission and skeletal transformations (isomerization and cyclization) determine the overall rates of depolymerization and aromatic formation.

KW - SDG11: Sustainable cities and communities

KW - SDG12: Responsible consumption and production

KW - SDG9: Industry, innovation, and infrastructure

KW - aromatization

KW - bifunctional catalyst

KW - depolymerization

KW - nanoscale reaction coupling

KW - plastic waste

KW - polyethylene upcycling

KW - tandem reaction

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DO - 10.1016/j.chempr.2023.05.017

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JO - Chem

JF - Chem

IS - 8

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Bifunctional tandem catalytic upcycling of polyethylene to surfactant-range alkylaromatics

Abstract

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