Mechanistic Insights into Processive Polyethylene Hydrogenolysis throughIn SituNMR

• DOI: 10.1021/acs.macromol.3c00474
• Publication Date: 2023-05-30T19:46:57Z
• Authors: Tommy Yunpu Zhao; Max Meirow; Akalanka Tennakoon; Xun Wu; Alexander L. Pate...; Long Qi; Anne M. LaPointe; Jessica V. Lamb; Takeshi Kobayashi; Massimiliano Delf...; Aaron D. Sadow; Wenyu Huang; Erik Luijten; Frédéric A. Perras
• Keywords: Polyolefin; Magic angle spinning; Hydrogenolysis

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