4.2 Article

Polyethylene Hydrogenolysis at Mild Conditions over Ruthenium on Tungstated Zirconia

Journal

JACS AU
Volume 1, Issue 9, Pages 1422-1434

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacsau.1c00200

Keywords

plastic waste; hydrogenolysis; low-density polyethylene; ruthenium; tungstated zirconia; hydrogen spillover

Funding

  1. Center for Plastics Innovation, an Energy Frontier Research Center - U.S. Dept. of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0021166]
  2. National Science Foundation [NNCI-1542153]
  3. NSF through the University of Pennsylvania Materials Research Science and Engineering Center (MRSEC) [DMR-1720530]
  4. NSLS II, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory [DE-SC0012704]
  5. Synchrotron Catalysis Consortium (U.S. DOE, Office of Basic Energy Sciences) [DE-SC0012335]

Ask authors/readers for more resources

The study demonstrates that using Ru-WZr as a hydrogenolysis catalyst can effectively suppress methane formation and produce products in the diesel and wax/lubricant base-oil range. The enhanced performance of the catalyst is showcased in single-use LDPE consumables, providing a new approach for environmentally friendly plastic recycling.
Plastics waste has become a major environmental threat, with polyethylene being one of the most produced and hardest to recycle plastics. Hydrogenolysis is potentially the most viable catalytic technology for recycling. Ruthenium (Ru) is one of the most active hydrogenolysis catalysts but yields too much methane. Here we introduce ruthenium supported on tungstated zirconia (Ru-WZr) for hydrogenolysis of low-density polyethylene (LDPE). We show that the Ru-WZr catalysts suppress methane formation and produce a product distribution in the diesel and wax/lubricant base-oil range unattainable by Ru-Zr and other Ru-supported catalysts. Importantly, the enhanced performance is showcased for real-world, single-use LDPE consumables. Reactivity studies combined with characterization and density functional theory calculations reveal that highly dispersed (WOx)(n) clusters store H as surface hydroxyls by spillover. We correlate this hydrogen storage mechanism with hydrogenation and desorption of long alkyl intermediates that would otherwise undergo further C-C scission to produce methane.

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