Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis

Shaojiang Chen; Akalanka Tennakoon; Kyung Eun You; Alexander L. Paterson; Ryan Yappert; Selim Alayoglu; Lingzhe Fang; Xun Wu; Tommy Yunpu Zhao; Michelle P. Lapak; Mukunth Saravanan; Ryan A. Hackler; Yi Yu Wang; Long Qi; Massimiliano Delferro; Tao Li; Byeongdu Lee; Baron Peters; Kenneth R. Poeppelmeier; Salai C. Ammal; Clifford R. Bowers; Frédéric A. Perras; Andreas Heyden; Aaron D. Sadow; Wenyu Huang

doi:10.1038/s41929-023-00910-x

Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis

Shaojiang Chen, Akalanka Tennakoon, Kyung Eun You, Alexander L. Paterson, Ryan Yappert, Selim Alayoglu, Lingzhe Fang, Xun Wu, Tommy Yunpu Zhao, Michelle P. Lapak, Mukunth Saravanan, Ryan A. Hackler, Yi Yu Wang, Long Qi, Massimiliano Delferro, Tao Li, Byeongdu Lee, Baron Peters, Kenneth R. Poeppelmeier, Salai C. AmmalClifford R. Bowers, Frédéric A. Perras, Andreas Heyden^*, Aaron D. Sadow^*, Wenyu Huang^*

^*Corresponding author for this work

Chemistry

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

73 Scopus citations

Abstract

Carbon–carbon bond cleavage reactions, adapted to deconstruct aliphatic hydrocarbon polymers and recover the intrinsic energy and carbon value in plastic waste, have typically been catalysed by metal nanoparticles or air-sensitive organometallics. Metal oxides that serve as supports for these catalysts are typically considered to be inert. Here we show that Earth-abundant, non-reducible zirconia catalyses the hydrogenolysis of polyolefins with activity rivalling that of precious metal nanoparticles. To harness this unusual reactivity, our catalytic architecture localizes ultrasmall amorphous zirconia nanoparticles between two fused platelets of mesoporous silica. Macromolecules translocate from bulk through radial mesopores to the highly active zirconia particles, where the chains undergo selective hydrogenolytic cleavage into a narrow, C₁₈-centred distribution. Calculations indicated that C–H bond heterolysis across a Zr–O bond of a Zr(O)₂ adatom model for unsaturated surface sites gives a zirconium hydrocarbyl, which cleaves a C–C bond via β-alkyl elimination. [Figure not available: see fulltext.].

Original language	English (US)
Pages (from-to)	161-173
Number of pages	13
Journal	Nature Catalysis
Volume	6
Issue number	2
DOIs	https://doi.org/10.1038/s41929-023-00910-x
State	Published - Feb 2023

Funding

This work was supported by the Institute for Cooperative Upcycling of Plastics (iCOUP), an Energy Frontier Research Center funded by the US Department of Energy (DOE) Office of Basic Energy Sciences. The Ames Laboratory is operated by Iowa State University under contract DE-AC-02-07CH11358 (S.C., A.T., K.-E.Y., A.L.P., R.Y., M.S., B.P., K.R.P., S.C.A., F.A.P., A.H., A.D.S. and W.H.) and the Argonne National Laboratory is operated by the UChicago Argonne under contract DE-AC-02-06CH11357 (L.F., R.A.H., M.D., T.L. and B.L.). S.C.A. and A.H. acknowledge partial support from the South Carolina Smart State Center for Strategic Approaches to the Generation of Electricity (SAGE). The pH2 labelling experiments were supported by National Science Foundation grant CHE-2108306 (T.Y.Z., M.P.L. and C.R.B.) and the National High Magnetic Field Laboratory is supported by the National Science Foundation through NSF/DMR-2128556* and the state of Florida. This research used resources of the Advanced Photon Source, a DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract AC02-06CH11357 (L.F., T.L. and B.L.). Computational resources were provided by XSEDE Resources, located at the San Diego Supercomputer Center, and Texas Advanced Computing Center grant TG-CTS090100 (K.-E.Y., S.C.A. and A.H.), as well as the National Energy Research Scientific Computing Center (NERSC) under contract DE-AC02-05CH11231 (K.-E.Y., S.C.A. and A.H.). This work was supported by the Institute for Cooperative Upcycling of Plastics (iCOUP), an Energy Frontier Research Center funded by the US Department of Energy (DOE) Office of Basic Energy Sciences. The Ames Laboratory is operated by Iowa State University under contract DE-AC-02-07CH11358 (S.C., A.T., K.-E.Y., A.L.P., R.Y., M.S., B.P., K.R.P., S.C.A., F.A.P., A.H., A.D.S. and W.H.) and the Argonne National Laboratory is operated by the UChicago Argonne under contract DE-AC-02-06CH11357 (L.F., R.A.H., M.D., T.L. and B.L.). S.C.A. and A.H. acknowledge partial support from the South Carolina Smart State Center for Strategic Approaches to the Generation of Electricity (SAGE). The pH labelling experiments were supported by National Science Foundation grant CHE-2108306 (T.Y.Z., M.P.L. and C.R.B.) and the National High Magnetic Field Laboratory is supported by the National Science Foundation through NSF/DMR-2128556* and the state of Florida.. This research used resources of the Advanced Photon Source, a DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract AC02-06CH11357 (L.F., T.L. and B.L.). Computational resources were provided by XSEDE Resources, located at the San Diego Supercomputer Center, and Texas Advanced Computing Center grant TG-CTS090100 (K.-E.Y., S.C.A. and A.H.), as well as the National Energy Research Scientific Computing Center (NERSC) under contract DE-AC02-05CH11231 (K.-E.Y., S.C.A. and A.H.). 2

ASJC Scopus subject areas

Catalysis
Bioengineering
Biochemistry
Process Chemistry and Technology

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10.1038/s41929-023-00910-x

Cite this

Chen, S., Tennakoon, A., You, K. E., Paterson, A. L., Yappert, R., Alayoglu, S., Fang, L., Wu, X., Zhao, T. Y., Lapak, M. P., Saravanan, M., Hackler, R. A., Wang, Y. Y., Qi, L., Delferro, M., Li, T., Lee, B., Peters, B., Poeppelmeier, K. R., ... Huang, W. (2023). Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis. Nature Catalysis, 6(2), 161-173. https://doi.org/10.1038/s41929-023-00910-x

@article{99c38cc75a9f4ad5bc83e075db4c2284,

title = "Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis",

abstract = "Carbon–carbon bond cleavage reactions, adapted to deconstruct aliphatic hydrocarbon polymers and recover the intrinsic energy and carbon value in plastic waste, have typically been catalysed by metal nanoparticles or air-sensitive organometallics. Metal oxides that serve as supports for these catalysts are typically considered to be inert. Here we show that Earth-abundant, non-reducible zirconia catalyses the hydrogenolysis of polyolefins with activity rivalling that of precious metal nanoparticles. To harness this unusual reactivity, our catalytic architecture localizes ultrasmall amorphous zirconia nanoparticles between two fused platelets of mesoporous silica. Macromolecules translocate from bulk through radial mesopores to the highly active zirconia particles, where the chains undergo selective hydrogenolytic cleavage into a narrow, C18-centred distribution. Calculations indicated that C–H bond heterolysis across a Zr–O bond of a Zr(O)2 adatom model for unsaturated surface sites gives a zirconium hydrocarbyl, which cleaves a C–C bond via β-alkyl elimination. [Figure not available: see fulltext.].",

author = "Shaojiang Chen and Akalanka Tennakoon and You, {Kyung Eun} and Paterson, {Alexander L.} and Ryan Yappert and Selim Alayoglu and Lingzhe Fang and Xun Wu and Zhao, {Tommy Yunpu} and Lapak, {Michelle P.} and Mukunth Saravanan and Hackler, {Ryan A.} and Wang, {Yi Yu} and Long Qi and Massimiliano Delferro and Tao Li and Byeongdu Lee and Baron Peters and Poeppelmeier, {Kenneth R.} and Ammal, {Salai C.} and Bowers, {Clifford R.} and Perras, {Fr{\'e}d{\'e}ric A.} and Andreas Heyden and Sadow, {Aaron D.} and Wenyu Huang",

note = "Funding Information: This work was supported by the Institute for Cooperative Upcycling of Plastics (iCOUP), an Energy Frontier Research Center funded by the US Department of Energy (DOE) Office of Basic Energy Sciences. The Ames Laboratory is operated by Iowa State University under contract DE-AC-02-07CH11358 (S.C., A.T., K.-E.Y., A.L.P., R.Y., M.S., B.P., K.R.P., S.C.A., F.A.P., A.H., A.D.S. and W.H.) and the Argonne National Laboratory is operated by the UChicago Argonne under contract DE-AC-02-06CH11357 (L.F., R.A.H., M.D., T.L. and B.L.). S.C.A. and A.H. acknowledge partial support from the South Carolina Smart State Center for Strategic Approaches to the Generation of Electricity (SAGE). The pH labelling experiments were supported by National Science Foundation grant CHE-2108306 (T.Y.Z., M.P.L. and C.R.B.) and the National High Magnetic Field Laboratory is supported by the National Science Foundation through NSF/DMR-2128556* and the state of Florida.. This research used resources of the Advanced Photon Source, a DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract AC02-06CH11357 (L.F., T.L. and B.L.). Computational resources were provided by XSEDE Resources, located at the San Diego Supercomputer Center, and Texas Advanced Computing Center grant TG-CTS090100 (K.-E.Y., S.C.A. and A.H.), as well as the National Energy Research Scientific Computing Center (NERSC) under contract DE-AC02-05CH11231 (K.-E.Y., S.C.A. and A.H.). 2 Publisher Copyright: {\textcopyright} 2023, The Author(s).",

year = "2023",

month = feb,

doi = "10.1038/s41929-023-00910-x",

language = "English (US)",

volume = "6",

pages = "161--173",

journal = "Nature Catalysis",

issn = "2520-1158",

publisher = "Nature Publishing Group",

number = "2",

}

Chen, S, Tennakoon, A, You, KE, Paterson, AL, Yappert, R, Alayoglu, S, Fang, L, Wu, X, Zhao, TY, Lapak, MP, Saravanan, M, Hackler, RA, Wang, YY, Qi, L, Delferro, M, Li, T, Lee, B, Peters, B, Poeppelmeier, KR, Ammal, SC, Bowers, CR, Perras, FA, Heyden, A, Sadow, AD & Huang, W 2023, 'Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis', Nature Catalysis, vol. 6, no. 2, pp. 161-173. https://doi.org/10.1038/s41929-023-00910-x

TY - JOUR

T1 - Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis

AU - Chen, Shaojiang

AU - Tennakoon, Akalanka

AU - You, Kyung Eun

AU - Paterson, Alexander L.

AU - Yappert, Ryan

AU - Alayoglu, Selim

AU - Fang, Lingzhe

AU - Wu, Xun

AU - Zhao, Tommy Yunpu

AU - Lapak, Michelle P.

AU - Saravanan, Mukunth

AU - Hackler, Ryan A.

AU - Wang, Yi Yu

AU - Qi, Long

AU - Delferro, Massimiliano

AU - Li, Tao

AU - Lee, Byeongdu

AU - Peters, Baron

AU - Poeppelmeier, Kenneth R.

AU - Ammal, Salai C.

AU - Bowers, Clifford R.

AU - Perras, Frédéric A.

AU - Heyden, Andreas

AU - Sadow, Aaron D.

AU - Huang, Wenyu

N1 - Funding Information: This work was supported by the Institute for Cooperative Upcycling of Plastics (iCOUP), an Energy Frontier Research Center funded by the US Department of Energy (DOE) Office of Basic Energy Sciences. The Ames Laboratory is operated by Iowa State University under contract DE-AC-02-07CH11358 (S.C., A.T., K.-E.Y., A.L.P., R.Y., M.S., B.P., K.R.P., S.C.A., F.A.P., A.H., A.D.S. and W.H.) and the Argonne National Laboratory is operated by the UChicago Argonne under contract DE-AC-02-06CH11357 (L.F., R.A.H., M.D., T.L. and B.L.). S.C.A. and A.H. acknowledge partial support from the South Carolina Smart State Center for Strategic Approaches to the Generation of Electricity (SAGE). The pH labelling experiments were supported by National Science Foundation grant CHE-2108306 (T.Y.Z., M.P.L. and C.R.B.) and the National High Magnetic Field Laboratory is supported by the National Science Foundation through NSF/DMR-2128556* and the state of Florida.. This research used resources of the Advanced Photon Source, a DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract AC02-06CH11357 (L.F., T.L. and B.L.). Computational resources were provided by XSEDE Resources, located at the San Diego Supercomputer Center, and Texas Advanced Computing Center grant TG-CTS090100 (K.-E.Y., S.C.A. and A.H.), as well as the National Energy Research Scientific Computing Center (NERSC) under contract DE-AC02-05CH11231 (K.-E.Y., S.C.A. and A.H.). 2 Publisher Copyright: © 2023, The Author(s).

PY - 2023/2

Y1 - 2023/2

N2 - Carbon–carbon bond cleavage reactions, adapted to deconstruct aliphatic hydrocarbon polymers and recover the intrinsic energy and carbon value in plastic waste, have typically been catalysed by metal nanoparticles or air-sensitive organometallics. Metal oxides that serve as supports for these catalysts are typically considered to be inert. Here we show that Earth-abundant, non-reducible zirconia catalyses the hydrogenolysis of polyolefins with activity rivalling that of precious metal nanoparticles. To harness this unusual reactivity, our catalytic architecture localizes ultrasmall amorphous zirconia nanoparticles between two fused platelets of mesoporous silica. Macromolecules translocate from bulk through radial mesopores to the highly active zirconia particles, where the chains undergo selective hydrogenolytic cleavage into a narrow, C18-centred distribution. Calculations indicated that C–H bond heterolysis across a Zr–O bond of a Zr(O)2 adatom model for unsaturated surface sites gives a zirconium hydrocarbyl, which cleaves a C–C bond via β-alkyl elimination. [Figure not available: see fulltext.].

AB - Carbon–carbon bond cleavage reactions, adapted to deconstruct aliphatic hydrocarbon polymers and recover the intrinsic energy and carbon value in plastic waste, have typically been catalysed by metal nanoparticles or air-sensitive organometallics. Metal oxides that serve as supports for these catalysts are typically considered to be inert. Here we show that Earth-abundant, non-reducible zirconia catalyses the hydrogenolysis of polyolefins with activity rivalling that of precious metal nanoparticles. To harness this unusual reactivity, our catalytic architecture localizes ultrasmall amorphous zirconia nanoparticles between two fused platelets of mesoporous silica. Macromolecules translocate from bulk through radial mesopores to the highly active zirconia particles, where the chains undergo selective hydrogenolytic cleavage into a narrow, C18-centred distribution. Calculations indicated that C–H bond heterolysis across a Zr–O bond of a Zr(O)2 adatom model for unsaturated surface sites gives a zirconium hydrocarbyl, which cleaves a C–C bond via β-alkyl elimination. [Figure not available: see fulltext.].

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VL - 6

SP - 161

EP - 173

JO - Nature Catalysis

JF - Nature Catalysis

IS - 2

ER -

Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis

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ZrO2-catalyzed Hydrogenolysis of Polyolefins

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Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis

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ZrO2-catalyzed Hydrogenolysis of Polyolefins

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