Two Mesoporous Domains Are Better Than One for Catalytic Deconstruction of Polyolefins

Tennakoon, Akalanka; Wu, Xun; Meirow, Max; Howell, Daniel; Willmon, Jarod; Yu, Jiaqi; Lamb, Jessica V.; Delferro, Massimiliano Max; Luijten, Erik; Huang, Wenyu; Sadow, Aaron D.

doi:10.1021/jacs.3c05447

Two Mesoporous Domains Are Better Than One for Catalytic Deconstruction of Polyolefins

Journal Article · Fri Aug 04 00:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c05447· OSTI ID:1994517

Tennakoon, Akalanka ^[1]; Wu, Xun ^[1]; ^[2]; ^[3]; Willmon, Jarod ^[3]; Yu, Jiaqi ^[3]; ^[4]; ^[4]; ^[2]; ^[1]; ^[1]

Ames Laboratory, and Iowa State University, Ames, IA (United States)
Northwestern University, Evanston, IL (United States)
Iowa State University, Ames, IA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

Catalytic hydrogenolysis of polyolefins into valuable liquid, oil, or wax-like hydrocarbon chains for second-life applications is typically accompanied by the hydrogen-wasting co-formation of low value volatiles, notably methane, that increase greenhouse gas emissions. Catalytic sites confined at the bottom of mesoporous wells, under conditions in which the pore exerts the greatest influence over the mechanism, are capable of producing less gases than unconfined sites. A new architecture was designed to emphasize this pore effect, with the active platinum nanoparticles embedded between linear, hexagonal mesoporous silica and gyroidal cubic MCM-48 silica (mSiO₂/Pt/MCM-48). This catalyst deconstructs polyolefins selectively into ~C₂₀–C₄₀ paraffins and cleaves C–C bonds at a rate (TOF = 4.2 ± 0.3 s^–1) exceeding that of materials lacking these combined features while generating negligible volatile side products including methane. The time-independent product distribution is consistent with a processive mechanism for polymer deconstruction. In contrast to time- and polymer length-dependent products obtained from non-porous catalysts, mSiO₂/Pt/MCM-48 yields a C₂₈-centered Gaussian distribution of waxy hydrocarbons from polyolefins of varying molecular weight, composition, and physical properties, including low-density polyethylene, isotactic polypropylene, ultrahigh-molecular-weight polyethylene, and mixtures of multiple, post-industrial polyolefins. Here, coarse-grained simulation reveals that the porous-core architecture enables the paraffins to diffuse away from the active platinum site, preventing secondary reactions that produce gases.

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:: 1994517

Alternate ID(s):: OSTI ID: 2367273

Report Number(s):: IS-J-11,134

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 32 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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