Effect of reaction media on hydrogenolysis of polyethylene plastic waste: Polymer-surface interactions in small alkane/polymer blends

Zare, Mehdi; Kots, Pavel A.; Hinton, Zachary R.; Epps, III, Thomas H.; Korley, LaShanda T.J.; Caratzoulas, Stavros; Vlachos, Dionisios G.

doi:10.1016/j.apcatb.2024.123969

Effect of reaction media on hydrogenolysis of polyethylene plastic waste: Polymer-surface interactions in small alkane/polymer blends

Journal Article · Tue Mar 19 00:00:00 EDT 2024 · Applied Catalysis. B, Environmental

DOI:https://doi.org/10.1016/j.apcatb.2024.123969· OSTI ID:2324888

Zare, Mehdi ^[1]; Kots, Pavel A. ^[2]; Hinton, Zachary R. ^[2]; Epps, III, Thomas H. ^[2]; Korley, LaShanda T.J. ^[2]; Caratzoulas, Stavros ^[2]; Vlachos, Dionisios G. ^[2]

University of Delaware, Newark, DE (United States); University of Delaware
University of Delaware, Newark, DE (United States)

The polymer reaction media and its properties can be altered by recycling a fraction of liquid products or adding alkane solvents. Less clear is whether this strategy affects hydrogenolysis. Herein, we investigated the effect of short-chain alkanes C_n consisting of n carbons (n=8, 16, and 32) on the upcycling of high-density polyethylene (HDPE) plastic waste to lubricant-range products over Ru/TiO₂ catalysts by multiscale simulations and experiments. First, we trained a force field for polymer/surface interactions on a Ru₂₂ nanoparticle (NP) supported on TiO₂. Using replica exchange molecular dynamics simulations, we studied the effect of small hydrocarbons on the adsorption of a surrogate polymer, C₁₄₂, on the catalyst. We found segregation of long chains (C₁₄₂) at the catalyst surface due to the enthalpy gained by adsorbing more C-C bonds of the long chains, compensating for entropic losses upon adsorption. Short-chain molecules decrease the adsorbed carbons of long chains on the Ru NP due to blocking Ru active sites. Compared to the bulk chains, competitive adsorption results in a broader, heavy-tailed distribution of end-to-end distance of adsorbed chains. Our experiments demonstrated that catalyst activity declines significantly beyond simple dilution due to changes in polymer adsorption, and tuning the reaction media by creating suitable blends impacts hydrogenolysis. Density distributions for a 50:50%wt mixture of PP and PE show that PE chains are segregated at the surface, so they are prone to C-C bond breaking much faster than PP chains. H/D exchange experiments show preferential deuteration of PE, while CH₃ groups of PP remain undeuterated. Furthermore, this may be explained by the preferential sorption of PE over PP, leading to specific distribution in the polymer blend.

View Accepted Manuscript (DOE)

Research Organization:: University of Delaware, Newark, DE (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0021166

OSTI ID:: 2324888

Alternate ID(s):: OSTI ID: 2340209

Journal Information:: Applied Catalysis. B, Environmental, Journal Name: Applied Catalysis. B, Environmental Vol. 351; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Effect of reaction media on hydrogenolysis of polyethylene plastic waste: Polymer-surface interactions in small alkane/polymer blends

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