Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis
Date
2023-02-16
Authors
Chen, Shaojiang
Tennakoon, Akalanka
You, Kyung-Eun
Paterson, Alexander L.
Yappert, Ryan
Alayoglu, Selim
Fang, Lingzhe
Wu, Xun
Zhao, Tommy Yunpu
Lapak, Michelle P.
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Iowa State University Digital Repository, Ames IA (United States)
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.
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IS-J 11001
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article
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This article is published as Chen, Shaojiang, Akalanka Tennakoon, Kyung-Eun You, Alexander L. Paterson, Ryan Yappert, Selim Alayoglu, Lingzhe Fang et al. "Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis." Nature Catalysis (2023): 1-13.
DOI: 10.1038/s41929-023-00910-x.
Copyright 2023 The Author(s).
Attribution 4.0 International (CC BY 4.0).
Posted with permission.
DOE Contract Number(s): AC02-07CH11358; AC-02-06CH11357; AC02-05CH11231; CHE-2108306; TG-CTS090100.