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

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

Journal Article · Tue Apr 05 00:00:00 EDT 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]; ^[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.

View Accepted Manuscript (DOE)

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

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

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

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

References (48)

Tailoring the Shape of Metal Ad-Particles by Doping the Oxide Support Shao, Xiang; Prada, Stefano; Giordano, Livia Angewandte Chemie International Edition, Vol. 50, Issue 48 https://doi.org/10.1002/anie.201105355	journal	October 2011
Towards the Circular Economy: Converting Aromatic Plastic Waste Back to Arenes over a Ru/Nb ₂ O ₅ Catalyst Jing, Yaxuan; Wang, Yanqin; Furukawa, Shinya Angewandte Chemie International Edition, Vol. 60, Issue 10 https://doi.org/10.1002/anie.202011063	journal	January 2021
Regioselectivity and Reaction Mechanism of Ru-Catalyzed Hydrogenolysis of Squalane and Model Alkanes Nakagawa, Yoshinao; Oya, Shin-ichi; Kanno, Daisuke ChemSusChem, Vol. 10, Issue 1 https://doi.org/10.1002/cssc.201601204	journal	November 2016
Effect of Various Pretreatments on the Structure and Properties of Ruthenium Catalysts Bond, Geoffrey C.; Coq, Bernard; Dutartre, Roger Journal of Catalysis, Vol. 161, Issue 1 https://doi.org/10.1006/jcat.1996.0207	journal	June 1996
Effect of oxidation-reduction cycling on C2H6 hydrogenolysis: Comparison of Ru, Rh, Ir, Ni, Pt, and Pd on SiO2*1 Gao, S. Journal of Catalysis, Vol. 115, Issue 2 https://doi.org/10.1016/0021-9517(89)90040-7	journal	February 1989
Effect of carbon support and mean Pt particle size on hydrogen chemisorption by carbon-supported Pt ctalysts Pradoburguete, C. Journal of Catalysis, Vol. 128, Issue 2 https://doi.org/10.1016/0021-9517(91)90298-i	journal	April 1991
Olefins from polyolefins and mixed plastics by pyrolysis Kaminsky, W.; Schlesselmann, B.; Simon, C. Journal of Analytical and Applied Pyrolysis, Vol. 32 https://doi.org/10.1016/0165-2370(94)00830-t	journal	April 1995
Influence of the hydrocarbon structure on the hydrogenolysis of alkanes over rhodium/alumina catalysts Coq, Bernsrd; Figueras, Francois Journal of Molecular Catalysis, Vol. 40, Issue 1 https://doi.org/10.1016/0304-5102(87)80010-x	journal	April 1987
Low-temperature catalytic upgrading of waste polyolefinic plastics into liquid fuels and waxes Nakaji, Yosuke; Tamura, Masazumi; Miyaoka, Shuhei Applied Catalysis B: Environmental, Vol. 285 https://doi.org/10.1016/j.apcatb.2020.119805	journal	May 2021
Non-thermal plasma-assisted hydrogenolysis of polyethylene to light hydrocarbons Yao, Libo; King, Jaelynne; Wu, Dezhen Catalysis Communications, Vol. 150 https://doi.org/10.1016/j.catcom.2020.106274	journal	February 2021
Hydrogenation of CO2 to formic acid on supported ruthenium catalysts Hao, Cuiying; Wang, Shengping; Li, Maoshuai Catalysis Today, Vol. 160, Issue 1 https://doi.org/10.1016/j.cattod.2010.05.034	journal	February 2011
Deconstruction of high-density polyethylene into liquid hydrocarbon fuels and lubricants by hydrogenolysis over Ru catalyst Jia, Chuhua; Xie, Shaoqu; Zhang, Wanli Chem Catalysis, Vol. 1, Issue 2 https://doi.org/10.1016/j.checat.2021.04.002	journal	July 2021
Catalytical and thermal pyrolysis of polyolefins Kaminsky, Walter; Zorriqueta, Ignacio-Javier Nuñez Journal of Analytical and Applied Pyrolysis, Vol. 79, Issue 1-2 https://doi.org/10.1016/j.jaap.2006.11.005	journal	May 2007
Structure sensitivity of hydrogenolytic cleavage of endocyclic and exocyclic C–C bonds in methylcyclohexane over supported iridium particles Shi, Hui; Gutiérrez, Oliver Y.; Haller, Gary L. Journal of Catalysis, Vol. 297 https://doi.org/10.1016/j.jcat.2012.09.018	journal	January 2013
Structure–activity relationships in catalysis by metals: some aspects of particle size, bimetallic and supports effects Coq, Bernard; Figueras, François Coordination Chemistry Reviews, Vol. 178-180 https://doi.org/10.1016/s0010-8545(98)00058-7	journal	December 1998
Catalytic pyrolysis of polyethylene Bagri, Ranbir; Williams, Paul T. Journal of Analytical and Applied Pyrolysis, Vol. 63, Issue 1 https://doi.org/10.1016/s0165-2370(01)00139-5	journal	March 2002
Influence of the precursor and the support on the catalytic properties of ruthenium for alkane hydrogenolysis Coq, B.; Bittar, A.; Dutartre, R. Applied Catalysis, Vol. 60, Issue 1 https://doi.org/10.1016/s0166-9834(00)82170-3	journal	January 1990
Effects of Chain Length on the Mechanism and Rates of Metal-Catalyzed Hydrogenolysis of n -Alkanes Hibbitts, David D.; Flaherty, David W.; Iglesia, Enrique The Journal of Physical Chemistry C, Vol. 120, Issue 15 https://doi.org/10.1021/acs.jpcc.6b00323	journal	April 2016
Hydrogenolysis of Linear Low-Density Polyethylene during Heterogeneous Catalytic Hydrogen–Deuterium Exchange Ertem, S. Piril; Onuoha, C. Emmanuel; Wang, Huiqun Macromolecules, Vol. 53, Issue 14 https://doi.org/10.1021/acs.macromol.0c00696	journal	July 2020
Heterolytic Hydrogen Activation: Understanding Support Effects in Water–Gas Shift, Hydrodeoxygenation, and CO Oxidation Catalysis Nelson, Nicholas C.; Szanyi, János ACS Catalysis, Vol. 10, Issue 10 https://doi.org/10.1021/acscatal.0c01059	journal	April 2020
Polypropylene Plastic Waste Conversion to Lubricants over Ru/TiO ₂ Catalysts Kots, Pavel A.; Liu, Sibao; Vance, Brandon C. ACS Catalysis, Vol. 11, Issue 13 https://doi.org/10.1021/acscatal.1c00874	journal	June 2021
Upcycling Single-Use Polyethylene into High-Quality Liquid Products Celik, Gokhan; Kennedy, Robert M.; Hackler, Ryan A. ACS Central Science, Vol. 5, Issue 11 https://doi.org/10.1021/acscentsci.9b00722	journal	September 2019
Hydrogenolysis of Polypropylene and Mixed Polyolefin Plastic Waste over Ru/C to Produce Liquid Alkanes Rorrer, Julie E.; Troyano-Valls, Clara; Beckham, Gregg T. ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 35 https://doi.org/10.1021/acssuschemeng.1c03786	journal	July 2021
Gold Supported on Thin Oxide Films: From Single Atoms to Nanoparticles Risse, Thomas; Shaikhutdinov, Shamil; Nilius, Niklas Accounts of Chemical Research, Vol. 41, Issue 8 https://doi.org/10.1021/ar800078m	journal	August 2008
Catalytic Consequences of Particle Size and Chloride Promotion in the Ring-Opening of Cyclopentane on Pt/Al ₂ O ₃ Shi, Hui; Gutiérrez, Oliver Y.; Yang, Hao ACS Catalysis, Vol. 3, Issue 3 https://doi.org/10.1021/cs300636j	journal	January 2013
Carbon-hydrogen and hydrogen-hydrogen activation in transition metal complexes and on surfaces Saillard, Jean Yves; Hoffmann, Roald Journal of the American Chemical Society, Vol. 106, Issue 7 https://doi.org/10.1021/ja00319a020	journal	April 1984
Three-Site Model for Hydrogen Adsorption on Supported Platinum Particles: Influence of Support Ionicity and Particle Size on the Hydrogen Coverage Oudenhuijzen, Michiel K.; van Bokhoven, Jeroen A.; Miller, Jeffrey T. Journal of the American Chemical Society, Vol. 127, Issue 5 https://doi.org/10.1021/ja045286c	journal	February 2005
Transition-State Enthalpy and Entropy Effects on Reactivity and Selectivity in Hydrogenolysis of n -Alkanes Flaherty, David W.; Iglesia, Enrique Journal of the American Chemical Society, Vol. 135, Issue 49 https://doi.org/10.1021/ja4093743	journal	November 2013
Metal-Catalyzed C–C Bond Cleavage in Alkanes: Effects of Methyl Substitution on Transition-State Structures and Stability Flaherty, David W.; Hibbitts, David D.; Iglesia, Enrique Journal of the American Chemical Society, Vol. 136, Issue 27 https://doi.org/10.1021/ja5037429	journal	June 2014
Conversion of Polyolefin Waste to Liquid Alkanes with Ru-Based Catalysts under Mild Conditions Rorrer, Julie E.; Beckham, Gregg T.; Román-Leshkov, Yuriy JACS Au, Vol. 1, Issue 1 https://doi.org/10.1021/jacsau.0c00041	journal	December 2020
Unlocking the Catalytic Potential of TiO ₂ -Supported Pt Single Atoms for the Reverse Water–Gas Shift Reaction by Altering Their Chemical Environment Chen, Linxiao; Unocic, Raymond R.; Hoffman, Adam S. JACS Au, Vol. 1, Issue 7 https://doi.org/10.1021/jacsau.1c00111	journal	June 2021
Polyethylene Hydrogenolysis at Mild Conditions over Ruthenium on Tungstated Zirconia Wang, Cong; Xie, Tianjun; Kots, Pavel A. JACS Au, Vol. 1, Issue 9 https://doi.org/10.1021/jacsau.1c00200	journal	August 2021
Mechanistic Pathways for Methylcyclohexane Hydrogenolysis over Supported Ir Catalysts Shi, Hui; Gutiérrez, Oliver Y.; Zheng, Anmin The Journal of Physical Chemistry C, Vol. 118, Issue 36 https://doi.org/10.1021/jp505483e	journal	August 2014
Relation between Crystallite Size and Dispersion on Supported Metal Catalysts Borodziński, Andrzej; Bonarowska, Magdalena Langmuir, Vol. 13, Issue 21 https://doi.org/10.1021/la962103u	journal	October 1997
Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina Peterson, Eric J.; DeLaRiva, Andrew T.; Lin, Sen Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5885	journal	September 2014
Carboxyl intermediate formation via an in situ-generated metastable active site during water-gas shift catalysis Nelson, Nicholas C.; Nguyen, Manh-Thuong; Glezakou, Vassiliki-Alexandra Nature Catalysis, Vol. 2, Issue 10 https://doi.org/10.1038/s41929-019-0343-2	journal	September 2019
Catalytic upcycling of high-density polyethylene via a processive mechanism Tennakoon, Akalanka; Wu, Xun; Paterson, Alexander L. Nature Catalysis, Vol. 3, Issue 11 https://doi.org/10.1038/s41929-020-00519-4	journal	October 2020
Estimation of mean size and shape of small metal particles by EXAFS Jentys, Andreas Physical Chemistry Chemical Physics, Vol. 1, Issue 17 https://doi.org/10.1039/a904654b	journal	January 1999
Mild metal-catalyzed C–H activation: examples and concepts Gensch, T.; Hopkinson, M. N.; Glorius, F. Chemical Society Reviews, Vol. 45, Issue 10 https://doi.org/10.1039/c6cs00075d	journal	January 2016
Effect of reaction conditions on the hydrogenolysis of polypropylene and polyethylene into gas and liquid alkanes Chen, Linxiao; Zhu, Yifeng; Meyer, Laura C. Reaction Chemistry & Engineering, Vol. 7, Issue 4 https://doi.org/10.1039/d1re00431j	journal	January 2022
Hydrogenolysis of alkanes. Part 3.—Hydrogenolysis of n-hexane and methylcyclopentane over variously treated Ru/TiO2 catalysts Burch, Robert; Bond, Geoffrey C.; Rajaram, Raj R. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 82, Issue 6 https://doi.org/10.1039/f19868201985	journal	January 1986
Accumulation and fragmentation of plastic debris in global environments Barnes, David K. A.; Galgani, Francois; Thompson, Richard C. Philosophical Transactions of the Royal Society B: Biological Sciences, Vol. 364, Issue 1526 https://doi.org/10.1098/rstb.2008.0205	journal	July 2009
Crossover from Three-Dimensional to Two-Dimensional Geometries of Au Nanostructures on Thin MgO(001) Films: A Confirmation of Theoretical Predictions Sterrer, Martin; Risse, Thomas; Heyde, Markus Physical Review Letters, Vol. 98, Issue 20 https://doi.org/10.1103/physrevlett.98.206103	journal	May 2007
Production, use, and fate of all plastics ever made Geyer, Roland; Jambeck, Jenna R.; Law, Kara Lavender Science Advances, Vol. 3, Issue 7 https://doi.org/10.1126/sciadv.1700782	journal	July 2017
Alkali-Stabilized Pt-OHx Species Catalyze Low-Temperature Water-Gas Shift Reactions Zhai, Y.; Pierre, D.; Si, R. Science, Vol. 329, Issue 5999 https://doi.org/10.1126/science.1192449	journal	September 2010
Thermally stable single-atom platinum-on-ceria catalysts via atom trapping Jones, J.; Xiong, H.; DeLaRiva, A. T. Science, Vol. 353, Issue 6295 https://doi.org/10.1126/science.aaf8800	journal	July 2016
Activation of surface lattice oxygen in single-atom Pt/CeO ₂ for low-temperature CO oxidation Nie, Lei; Mei, Donghai; Xiong, Haifeng Science, Vol. 358, Issue 6369 https://doi.org/10.1126/science.aao2109	journal	December 2017
Polyethylene upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization Zhang, Fan; Zeng, Manhao; Yappert, Ryan D. Science, Vol. 370, Issue 6515 https://doi.org/10.1126/science.abc5441	journal	October 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
plastic upcycling
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