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Size-Controlled Nanoparticles Embedded in a Mesoporous Architecture Leading to Efficient and Selective Hydrogenolysis of Polyolefins

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.1c11694· OSTI ID:1856850
 [1];  [1];  [2];  [3];  [4];  [4];  [5];  [6];  [4];  [2];  [1];  [1]
  1. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
  2. Univ. of Illinois at Urbana-Champaign, IL (United States)
  3. Iowa State Univ., Ames, IA (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Cornell Univ., Ithaca, NY (United States)
  6. Department of Chemical Engineering, University of South Carolina, Columbia, South Carolina 29208, United States
+ Show Author Affiliations
A catalytic architecture, comprising a mesoporous silica shell surrounding platinum nanoparticles (NPs) supported on a solid silica sphere (mSiO2/Pt-X/SiO2; X is the mean NP diameter), catalyzes hydrogenolysis of melt-phase polyethylene (PE) into a narrow C23-centered distribution of hydrocarbons in high yield using very low Pt loadings (~10-5 g Pt/g PE). During catalysis, a polymer chain enters a pore and contacts a Pt NP where the C–C bond cleavage occurs and then the smaller fragment exits the pore. mSiO2/Pt/SiO2 resists sintering or leaching of Pt and provides high yields of liquids; however, many structural and chemical effects on catalysis are not yet resolved. Here, we report the effects of Pt NP size on activity and selectivity in PE hydrogenolysis. Time-dependent conversion and yields and a lumped kinetics model based on the competitive adsorption of long vs short chains reveal that the activity of catalytic material is highest with the smallest NPs, consistent with a structure-sensitive reaction. Remarkably, the three mSiO2/Pt-X/SiO2 catalysts give equivalent selectivity. We propose that mesoscale pores in the catalytic architecture template the C23-centered distribution, whereas the active Pt sites influence the carbon–carbon bond cleavage rate. This conclusion provides a framework for catalyst design by separating the C–C bond cleavage activity at catalytic sites from selectivity for chain lengths of the products influenced by the structure of the catalytic architecture. The increased activity, selectivity, efficiency, and lifetime obtained using this architecture highlight the benefits of localized and confined environments for isolated catalytic particles under condensed-phase reaction conditions.
Research Organization:
Ames Laboratory (AMES), Ames, IA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Cooperative Upcycling of Plastics (iCOUP)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-06CH11357; AC02-07CH11358
OSTI ID:
1856850
Alternate ID(s):
OSTI ID: 1864280
OSTI ID: 1958429
Report Number(s):
IS-J-10,732; IS-J-10,751
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 12 Vol. 144; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Platinum
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redox reactions