Conformations of polyolefins on platinum catalysts control product distribution in plastics recycling
| Author(s) | Zare, Mehdi | |
| Author(s) | Kots, Pavel A. | |
| Author(s) | Caratzoulas, Stavros | |
| Author(s) | Vlachos, Dionisios G. | |
| Date Accessioned | 2024-03-04T19:00:38Z | |
| Date Available | 2024-03-04T19:00:38Z | |
| Publication Date | 2023-01-03 | |
| Description | This article was originally published in Chemical Science. The version of record is available at: https://doi.org/10.1039/D2SC04772A. © 2023 The Author(s). Published by the Royal Society of Chemistry | |
| Abstract | The design of catalysts for the chemical recycling of plastic waste will benefit greatly from an intimate knowledge of the interfacial polymer–catalyst interactions that determine reactant and product distributions. Here, we investigate backbone chain length, side chain length, and concentration effects on the density and conformation of polyethylene surrogates at the interface with Pt(111) and relate them to experimental product distributions resulting from carbon–carbon bond cleavage. Using replica-exchange molecular dynamics simulations, we characterize the polymer conformations at the interface by the distributions of trains, loops, and tails and their first moments. We find that the preponderance of short chains, in the range of 20 carbon atoms, lies entirely on the Pt surface, whereas longer chains exhibit much broader distributions of conformational features. Remarkably, the average length of trains is independent of the chain length but can be tuned via the polymer–surface interaction. Branching profoundly impacts the conformations of long chains at the interface as the distributions of trains become less dispersed and more structured, localized around short trains, with the immediate implication of a wider carbon product distribution upon C–C bond cleavage. The degree of localization increases with the number and size of the side chains. Long chains can adsorb from the melt onto the Pt surface even in melt mixtures containing shorter polymer chains at high concentrations. We confirm experimentally key computational findings and demonstrate that blends may provide a strategy to reduce the selectivity for undesired light gases. | |
| Sponsor | This work was intellectually led and supported as part of the Center for Plastics Innovation, an Energy Frontier Research Center funded by the US Dept of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0021166. The code and data analysis were supported by Department of Energy's Office of Energy Efficiency and Renewable Energy and Advanced Manufacturing Office under Award Number DE-EE0007888-9.5. The Delaware Energy Institute gratefully acknowledges the support and partnership of the State of Delaware toward the RAPID projects. | |
| Citation | Zare, Mehdi, Pavel A. Kots, Stavros Caratzoulas, and Dionisios G. Vlachos. “Conformations of Polyolefins on Platinum Catalysts Control Product Distribution in Plastics Recycling.” Chemical Science 14, no. 8 (2023): 1966–77. https://doi.org/10.1039/D2SC04772A. | |
| ISSN | 2041-6539 | |
| URL | https://udspace.udel.edu/handle/19716/34093 | |
| Language | en_US | |
| Publisher | Chemical Science | |
| dc.rights | Attribution-NonCommercial 3.0 Unported | en |
| dc.rights.uri | https://creativecommons.org/licenses/by-nc/3.0/ | |
| Keywords | responsible consumption and production | |
| Title | Conformations of polyolefins on platinum catalysts control product distribution in plastics recycling | |
| Type | Article |
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