Mechanistic Insights into Processive Polyethylene Hydrogenolysis through In Situ NMR

Zhao, Tommy Yunpu; Meirow, Max; Tennakoon, Akalanka; Wu, Xun; Paterson, Alexander; Qi, Long; LaPointe, Anne; Lamb, Jessica; Kobayashi, Takeshi; Delferro, Massimiliano; Sadow, Aaron; Huang, Wenyu; Luijten, Erik; Perras, Frederic

doi:10.1021/acs.macromol.3c00474

Mechanistic Insights into Processive Polyethylene Hydrogenolysis through In Situ NMR

Journal Article · Tue May 30 00:00:00 EDT 2023 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.3c00474· OSTI ID:1975937

Zhao, Tommy Yunpu ^[1]; Meirow, Max ^[2]; Tennakoon, Akalanka ^[3]; Wu, Xun ^[3]; Paterson, Alexander ^[1]; Qi, Long ^[1]; LaPointe, Anne ^[4]; Lamb, Jessica ^[5]; Kobayashi, Takeshi ^[1]; Delferro, Massimiliano ^[5]; Sadow, Aaron ^[3]; Huang, Wenyu ^[3]; Luijten, Erik ^[2]; Perras, Frederic ^[3]

Ames Laboratory (AMES), Ames, IA (United States)
Northwestern Univ., Evanston, IL (United States)
Ames Laboratory (AMES), Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
Cornell Univ., Ithaca, NY (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

Chemical polymer upcycling by processive catalysts is a promising plastic waste remediation strategy, with the capability of producing selective, high-value products from waste plastics with minimal energy input. We previously designed a novel processive catalyst with a mesoporous SiO₂ shell/Pt nanoparticle/SiO₂ core architecture (mSiO₂/Pt/SiO₂) that deconstructs polyolefins within narrow pores. Here, in this paper, we elucidate the mechanism of processive polyolefin hydrogenolysis using in situ magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and coarse-grained molecular dynamics simulations. We observe that most polyethylene–Pt interactions do not lead to C–C bond cleavage but rather to the release of the polymer via a dehydrogenation–rehydrogenation cycle. The porous architecture increases the likelihood that a released polymer is later cleaved and enables the catalyst to perform multiple successive cleavages to the same polymer chain. Both experiment and simulation show that the extent of processivity is strongly correlated with the length of the pores, with longer pores leading to a higher processivity.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-07CH11358; AC02-06CH11357

OSTI ID:: 1975937

Alternate ID(s):: OSTI ID: 2310920

Report Number(s):: IS-J--11,070

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 11 Vol. 56; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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