Disordered, Sub-Nanometer Ru Structures on CeO2 are Highly Efficient and Selective Catalysts in Polymer Upcycling by Hydrogenolysis

Chen, Linxiao; Meyer, Laura C.; Kovarik, Libor; Meira, Debora; Pereira-Hernandez, Xavier I.; Shi, Honghong; Khivantsev, Konstantin; Gutiérrez, Oliver Y.; Szanyi, János

doi:10.1021/acscatal.2c00684

Title: Disordered, Sub-Nanometer Ru Structures on CeO₂ are Highly Efficient and Selective Catalysts in Polymer Upcycling by Hydrogenolysis

Journal Article · 04 April 2022 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.2c00684 · OSTI ID:1862990

Chen, Linxiao ^[1]; Meyer, Laura C. ^[1]; Kovarik, Libor ^[1]; Meira, Debora ^[2]; Pereira-Hernandez, Xavier I. ^[1]; Shi, Honghong ^[1];

^[1];

^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Canadian Light Source Inc., Saskatoon (Canada)

We report non-degradable polyolefin plastics pose severe environmental threats, and thus demand efficient upcycling technologies. In this work, we discovered that low-loading (= 0.25 wt%) Ru/CeO₂ exhibits remarkable catalytic performance in the hydrogenolysis of polypropylene (PP), polyethylene (PE), and n-C₁₆H₃₄ that is superior to high-loading (= 0.5 wt%) Ru/CeO₂. They possess high PP conversion efficiency (7-fold increase over current literature reports), low selectivity towards undesired CH₄, and good isomerization ability. In the low-loading range, the intrinsic activity of Ru in PP hydrogenolysis increases as the particle size decreases, opposite of the trend in the high-loading range. Detailed characterization revealed that the abrupt changes in catalytic behaviors coincide with Ru species transitioning from well-defined to highly disordered structures in the low-loading domain. The disordered Ru species were shown to be sub-nanometer in size and cationic. Mechanistically, the regioselectivity and the rate dependence on hydrogen pressure of C-C bond cleavage are different on low- and high-loading Ru/CeO₂, both explained by the higher coverage of adsorbed hydrogen (*H) on low-loading Ru/CeO₂. This work uncovers the remarkable catalytic performance of highly disordered, sub-nanometer, cationic Ru species in polyolefin hydrogenolysis, opening immense opportunities to develop effective, selective, and versatile catalysts for plastic upcycling.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Canadian Light Source

Grant/Contract Number:: AC05-76RL01830; AC02-06CH11357

OSTI ID:: 1862990

Alternate ID(s):: OSTI ID: 1866433; OSTI ID: 1869880; OSTI ID: 1901269

Report Number(s):: PNNL-SA-170085

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 8 Vol. 12; ISSN 2155-5435

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
plastic upcycling
hydrogenolysis
polypropylene
polyethylene
ruthenium

Title: Disordered, Sub-Nanometer Ru Structures on CeO2 are Highly Efficient and Selective Catalysts in Polymer Upcycling by Hydrogenolysis

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References (48)

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Title: Disordered, Sub-Nanometer Ru Structures on CeO₂ are Highly Efficient and Selective Catalysts in Polymer Upcycling by Hydrogenolysis