Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis

Chen, Shaojiang; Tennakoon, Akalanka; You, Kyung-Eun; Paterson, Alexander L.; Yappert, Ryan; Alayoglu, Selim; Fang, Lingzhe; Wu, Xun; Zhao, Tommy Yunpu; Lapak, Michelle P.; Saravanan, Mukunth; Hackler, Ryan A.; Wang, Yi-Yu; Qi, Long; Delferro, Massimiliano; Li, Tao; Lee, Byeongdu; Peters, Baron; Poeppelmeier, Kenneth R.; Ammal, Salai C.; Bowers, Clifford R.; Perras, Frédéric A.; Heyden, Andreas; Sadow, Aaron D.; Huang, Wenyu

doi:10.1038/s41929-023-00910-x

Title: Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis

Journal Article · 15 February 2023 · Nature Catalysis

DOI: https://doi.org/10.1038/s41929-023-00910-x · OSTI ID:1959193

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Ames Lab., and Iowa State Univ., Ames, IA (United States)
Univ. of South Carolina, Columbia, SC (United States)
Univ. of Illinois at Urbana-Champaign, IL (United States)
Northwestern Univ., Evanston, IL (United States)
Northern Illinois Univ., DeKalb, IL (United States)
Univ. of Florida, Gainesville, FL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)
Northern Illinois Univ., DeKalb, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Florida, Gainesville, FL (United States). National High Magnetic Field Lab. (MagLab)

Carbon–carbon bond cleavage reactions, adapted to deconstruct aliphatic hydrocarbon polymers and recover the intrinsic energy and carbon value in plastic waste, have typically been catalysed by metal nanoparticles or air-sensitive organometallics. Metal oxides that serve as supports for these catalysts are typically considered to be inert. Here we show that Earth-abundant, non-reducible zirconia catalyses the hydrogenolysis of polyolefins with activity rivalling that of precious metal nanoparticles. To harness this unusual reactivity, our catalytic architecture localizes ultrasmall amorphous zirconia nanoparticles between two fused platelets of mesoporous silica. Macromolecules translocate from bulk through radial mesopores to the highly active zirconia particles, where the chains undergo selective hydrogenolytic cleavage into a narrow, C18-centred distribution. Calculations indicated that C–H bond heterolysis across a Zr–O bond of a Zr(O)₂ adatom model for unsaturated surface sites gives a zirconium hydrocarbyl, which cleaves a C–C bond via β-alkyl elimination.

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Research Organization:: Ames Laboratory (AMES), Ames, IA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: AC02-07CH11358; AC02-06CH11357; AC02-05CH11231

OSTI ID:: 1959193

Alternate ID(s):: OSTI ID: 2283551

Report Number(s):: IS-J--11,001; {"","Journal ID: ISSN 2520-1158"}

Journal Information:: Nature Catalysis, Journal Name: Nature Catalysis Journal Issue: 2 Vol. 6; ISSN 2520-1158

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

Natural Abundance ¹⁷ O DNP Two-Dimensional and Surface-Enhanced NMR Spectroscopy Perras, Frédéric A.; Kobayashi, Takeshi; Pruski, Marek Journal of the American Chemical Society, Vol. 137, Issue 26 https://doi.org/10.1021/jacs.5b03905	journal	June 2015
Surface Enhanced NMR Spectroscopy by Dynamic Nuclear Polarization Lesage, Anne; Lelli, Moreno; Gajan, David Journal of the American Chemical Society, Vol. 132, Issue 44 https://doi.org/10.1021/ja104771z	journal	November 2010
¹⁷O Solid-State NMR Studies of ZrO₂ Nanoparticles Shen, Li; Wu, Xin-Ping; Wang, Yang The Journal of Physical Chemistry C, Vol. 123, Issue 7 https://doi.org/10.1021/acs.jpcc.8b11091	journal	January 2019
Catalytic Hydrogenolysis at Low Temperature and Pressure of Polyethylene and Polypropylene to Diesels or Lower Alkanes by a Zirconium Hydride Supported on Silica-Alumina: A Step Toward Polyolefin Degradation by the Microscopic Reverse of Ziegler-Natta Polymerization Dufaud, Véronique; Basset, Jean-Marie Angewandte Chemie International Edition, Vol. 37, Issue 6 https://doi.org/10.1002/(SICI)1521-3773(19980403)37:6<806::AID-ANIE806>3.0.CO;2-6	journal	April 1998
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
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
Simplified method for calculating the energy of weakly interacting fragments Harris, J. Physical Review B, Vol. 31, Issue 4 https://doi.org/10.1103/PhysRevB.31.1770	journal	February 1985
Infrared studies of ethene hydrogenation over ZrO ₂ . Part 3.—Reaction mechanism Kondo, Junko; Domen, Kazunari; Maruya, Ken-ichi J. Chem. Soc., Faraday Trans., Vol. 88, Issue 14 https://doi.org/10.1039/FT9928802095	journal	January 1992
Silica-Encapsulated Pt-Sn Intermetallic Nanoparticles: A Robust Catalytic Platform for Parahydrogen-Induced Polarization of Gases and Liquids Zhao, Evan W.; Maligal-Ganesh, Raghu; Xiao, Chaoxian Angewandte Chemie International Edition, Vol. 56, Issue 14 https://doi.org/10.1002/anie.201701314	journal	March 2017
Methane and benzene activation via transient (tert-Bu3SiNH)2Zr:NSi-tert-Bu3 Cummins, Christopher C.; Baxter, Steven M.; Wolczanski, Peter T. Journal of the American Chemical Society, Vol. 110, Issue 26 https://doi.org/10.1021/ja00234a044	journal	December 1988
Catalysis over Supported Metals. III. Comparison of Metals of Known Surface Area for Ethane Hydrogenolysis Sinfelt, J. H.; Taylor, W. F.; Yates, D. J. C. The Journal of Physical Chemistry, Vol. 69, Issue 1 https://doi.org/10.1021/j100885a016	journal	January 1965
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
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
I.r. spectra of hydrogen adsorbed on ZrO2 Onishi, Takaharu; Abe, Hiroshi; Maruya, Ken-ichi Journal of the Chemical Society, Chemical Communications, Issue 9 https://doi.org/10.1039/c39850000617	journal	January 1985
Atomic-scale structure of amorphous TiO2 by electron, X-ray diffraction and reverse Monte Carlo simulations Petkov, V.; Holzhüter, G.; Tröge, U. Journal of Non-Crystalline Solids, Vol. 231, Issue 1-2 https://doi.org/10.1016/S0022-3093(98)00418-9	journal	July 1998
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Nature of Acid Sites in Silica-Supported Zirconium Oxide: A Combined Experimental and Periodic DFT Study Arce-Ramos, Juan-Manuel; Grabow, Lars C.; Handy, Brent E. The Journal of Physical Chemistry C, Vol. 119, Issue 27 https://doi.org/10.1021/acs.jpcc.5b02394	journal	June 2015
Control of coordinatively unsaturated Zr sites in ZrO2 for efficient C–H bond activation Zhang, Yaoyuan; Zhao, Yun; Otroshchenko, Tatiana Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-06174-5	journal	September 2018
Direct ¹⁷ O dynamic nuclear polarization of single-site heterogeneous catalysts Perras, Frédéric A.; Boteju, Kasuni C.; Slowing, Igor I. Chemical Communications, Vol. 54, Issue 28 https://doi.org/10.1039/C8CC00293B	journal	January 2018
Zr ₆ O ₈ Node-Catalyzed Butene Hydrogenation and Isomerization in the Metal–Organic Framework NU-1000 Hicks, Kenton E.; Rosen, Andrew S.; Syed, Zoha H. ACS Catalysis, Vol. 10, Issue 24 https://doi.org/10.1021/acscatal.0c03579	journal	December 2020
Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method Heyden, Andreas; Bell, Alexis T.; Keil, Frerich J. The Journal of Chemical Physics, Vol. 123, Issue 22 https://doi.org/10.1063/1.2104507	journal	December 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
Graphene-Based Nanosheets with a Sandwich Structure Yang, Shubin; Feng, Xinliang; Wang, Long Angewandte Chemie International Edition, Vol. 49, Issue 28 https://doi.org/10.1002/anie.201001634	journal	May 2010
Catalytic carbon-carbon bond cleavage and carbon-element bond formation give new life for polyolefins as biodegradable surfactants Kanbur, Uddhav; Zang, Guiyan; Paterson, Alexander L. Chem, Vol. 7, Issue 5 https://doi.org/10.1016/j.chempr.2021.03.007	journal	May 2021
Turning a Nonreducible into a Reducible Oxide via Nanostructuring: Opposite Behavior of Bulk ZrO ₂ and ZrO ₂ Nanoparticles Toward H ₂ Adsorption Ruiz Puigdollers, Antonio; Tosoni, Sergio; Pacchioni, Gianfranco The Journal of Physical Chemistry C, Vol. 120, Issue 28 https://doi.org/10.1021/acs.jpcc.6b05984	journal	July 2016
Spatial distribution of organic functional groups supported on mesoporous silica nanoparticles: a study by conventional and DNP-enhanced ²⁹ Si solid-state NMR Kobayashi, Takeshi; Singappuli-Arachchige, Dilini; Wang, Zhuoran Physical Chemistry Chemical Physics, Vol. 19, Issue 3 https://doi.org/10.1039/C6CP07642D	journal	January 2017
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Hydrothermal preparation of a platinum-loaded sulphated nanozirconia catalyst for the effective conversion of waste low density polyethylene into gasoline-range hydrocarbons Utami, Maisari; Trisunaryanti, Wega; Shida, Kenji RSC Advances, Vol. 9, Issue 71 https://doi.org/10.1039/C9RA08834B	journal	January 2019
Catalytic Cleavage of the C-H and C-C Bonds of Alkanes by Surface Organometallic Chemistry: An EXAFS and IR Characterization of a Zr-H Catalyst Corker, J.; Lefebvre, F. d. r.; Evans, J. Science, Vol. 271, Issue 5251 https://doi.org/10.1126/science.271.5251.966	journal	February 1996
The structure sensitivity of n-heptane dehydrocyclization and hydrogenolysis catalyzed by platinum single crystals at atmospheric pressure Gillespie, W. Journal of Catalysis, Vol. 70, Issue 1 https://doi.org/10.1016/0021-9517(81)90324-9	journal	July 1981
The Structure and Properties of Amorphous Indium Oxide Buchholz, D. Bruce; Ma, Qing; Alducin, Diego Chemistry of Materials, Vol. 26, Issue 18 https://doi.org/10.1021/cm502689x	journal	September 2014
Parahydrogen and synthesis allow dramatically enhanced nuclear alignment Bowers, C. Russell; Weitekamp, D. P. Journal of the American Chemical Society, Vol. 109, Issue 18 https://doi.org/10.1021/ja00252a049	journal	September 1987
Catalytic Hydrocracking-Mechanisms and Versatility of the Process Weitkamp, Jens ChemCatChem, Vol. 4, Issue 3 https://doi.org/10.1002/cctc.201100315	journal	February 2012
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
Understanding Selective Hydrodeoxygenation of 1,2- and 1,3-Propanediols on Cu/Mo₂C via Multiscale Modeling You, Kyung-Eun; Ammal, Salai C.; Lin, Zhexi ACS Catalysis, Vol. 12, Issue 8 https://doi.org/10.1021/acscatal.2c00261	journal	April 2022
Sandwich-Type Nanocomposite of Reduced Graphene Oxide and Periodic Mesoporous Silica with Vertically Aligned Mesochannels of Tunable Pore Depth and Size Wang, Zheng-Ming; Peng, Wenqin; Takenaka, Yoshiko Advanced Functional Materials, Vol. 27, Issue 47 https://doi.org/10.1002/adfm.201704066	journal	October 2017
Generation, alkyne cycloaddition, arene carbon-hydrogen activation, nitrogen-hydrogen activation and dative ligand trapping reactions of the first monomeric imidozirconocene (Cp2Zr:NR) complexes Walsh, Patrick J.; Hollander, Frederick J.; Bergman, Robert G. Journal of the American Chemical Society, Vol. 110, Issue 26 https://doi.org/10.1021/ja00234a043	journal	December 1988
β-Alkyl Elimination: Fundamental Principles and Some Applications O’Reilly, Matthew E.; Dutta, Saikat; Veige, Adam S. Chemical Reviews, Vol. 116, Issue 14 https://doi.org/10.1021/acs.chemrev.6b00054	journal	June 2016
Size-Controlled Nanoparticles Embedded in a Mesoporous Architecture Leading to Efficient and Selective Hydrogenolysis of Polyolefins Wu, Xun; Tennakoon, Akalanka; Yappert, Ryan Journal of the American Chemical Society, Vol. 144, Issue 12 https://doi.org/10.1021/jacs.1c11694	journal	February 2022
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Plastic waste to fuels by hydrocracking at mild conditions Liu, Sibao; Kots, Pavel A.; Vance, Brandon C. Science Advances, Vol. 7, Issue 17 https://doi.org/10.1126/sciadv.abf8283	journal	April 2021
Effect of hydrogen treatments on ZrO2 and Pt/ZrO2 catalysts Hoang, D. L.; Lieske, H. Catalysis Letters, Vol. 27, Issue 1-2 https://doi.org/10.1007/BF00806975	journal	January 1994
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Periodic boundary conditions in ab initio calculations Makov, G.; Payne, M. C. Physical Review B, Vol. 51, Issue 7 https://doi.org/10.1103/PhysRevB.51.4014	journal	February 1995
Net NMR alignment by adiabatic transport of parahydrogen addition products to high magnetic field Pravica, Michael G.; Weitekamp, Daniel P. Chemical Physics Letters, Vol. 145, Issue 4 https://doi.org/10.1016/0009-2614(88)80002-2	journal	April 1988
Intrinsic charge trapping in amorphous oxide films: status and challenges Strand, Jack; Kaviani, Moloud; Gao, David Journal of Physics: Condensed Matter, Vol. 30, Issue 23 https://doi.org/10.1088/1361-648X/aac005	journal	May 2018
Olefin Metathesis by Supported Metal Oxide Catalysts Lwin, Soe; Wachs, Israel E. ACS Catalysis, Vol. 4, Issue 8 https://doi.org/10.1021/cs500528h	journal	June 2014
Direct Conversion of Polypropylene into Liquid Hydrocarbons on Carbon‐Supported Platinum Catalysts Jaydev, Shibashish D.; Martín, Antonio J.; Pérez‐Ramírez, Javier ChemSusChem, Vol. 14, Issue 23 https://doi.org/10.1002/cssc.202101999	journal	October 2021
Graphene Oxide−Periodic Mesoporous Silica Sandwich Nanocomposites with Vertically Oriented Channels Wang, Zheng-Ming; Wang, Wendong; Coombs, Neil ACS Nano, Vol. 4, Issue 12 https://doi.org/10.1021/nn102618n	journal	November 2010
Structure of Amorphous Aluminum Oxide Lee, Sung Keun; Lee, Sung Bo; Park, Sun Young Physical Review Letters, Vol. 103, Issue 9 https://doi.org/10.1103/PhysRevLett.103.095501	journal	August 2009
The Entropies of Adsorbed Molecules Campbell, Charles T.; Sellers, Jason R. V. Journal of the American Chemical Society, Vol. 134, Issue 43 https://doi.org/10.1021/ja3080117	journal	October 2012
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
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

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Title: Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis

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