Size and Structure Effects of Carbon-Supported Ruthenium Nanoparticles on Waste Polypropylene Hydrogenolysis Activity, Selectivity, and Product Microstructure

Sun, Jessie A.; Kots, Pavel A.; Hinton, Zachary R.; Marinkovic, Nebojsa S.; Ma, Lu; Ehrlich, Steven N.; Zheng, Weiqing; Epps, Thomas H.; Korley, LaShanda T.J.; Vlachos, Dionisios G.

doi:10.1021/acscatal.3c05927

Size and Structure Effects of Carbon-Supported Ruthenium Nanoparticles on Waste Polypropylene Hydrogenolysis Activity, Selectivity, and Product Microstructure

Journal Article · Wed Feb 14 23:00:00 EST 2024 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.3c05927· OSTI ID:2432585

Sun, Jessie A. ^[1]; ^[1]; Hinton, Zachary R. ^[1]; ^[2]; Ma, Lu ^[3]; Ehrlich, Steven N. ^[3]; ^[1]; ^[1]; ^[1]; ^[1]

Univ. of Delaware, Newark, DE (United States)
Columbia Univ., New York, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Hydrogenolysis of plastic waste using Ru-based catalysts is promising for deconstructing polyolefins into lower molecular weight products. Yet, the effect of catalyst atomic structure and size on activity and product selectivity is poorly understood. Herein, we expose the effect of metal particle size and atomic structure on isotactic-polypropylene (i-PP) hydrogenolysis over Ru supported on carbon. Despite similar molecular weight distributions of solid and liquid products, their physical properties are distinct due to different chain regio-irregular CH3 sequences of steric pentads containing racemo configurations. We propose that i-PP hydrogenolysis entails an interplay of C–C bond scission and stereoisomerization. The active site’s local electronic environment and structure dictate the former, whereas polymer–catalyst surface interactions creating suitable polymer conformations control the latter. C–C scission and stereoisomerization are structure-sensitive. Small, disordered nanoclusters are effective in C–C bond scission, whereas larger metal nanoparticles promote stereoisomerization. Finally, we hypothesize that a heterogeneous distribution of metal active sites is essential for deconstruction and product (lubricant base oil) quality control.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2432585

Report Number(s):: BNL--225970-2024-JAAM

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 5 Vol. 14; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Size and Structure Effects of Carbon-Supported Ruthenium Nanoparticles on Waste Polypropylene Hydrogenolysis Activity, Selectivity, and Product Microstructure

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