Polyethylene Terephthalate Deconstruction Catalyzed by a Carbon‐Supported Single‐Site Molybdenum‐Dioxo Complex

Kratish, Yosi; Li, Jiaqi; Liu, Shanfu; Gao, Yanshan; Marks, Tobin J.

doi:10.1002/ange.202007423

Polyethylene Terephthalate Deconstruction Catalyzed by a Carbon‐Supported Single‐Site Molybdenum‐Dioxo Complex

Journal Article · Tue Sep 15 04:00:00 EDT 2020 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202007423· OSTI ID:1668096

Kratish, Yosi ^[1]; Li, Jiaqi ^[1]; Liu, Shanfu ^[1]; Gao, Yanshan ^[1]; ^[1]

Department of Chemistry and the Institute for Catalysis in Energy Processes (ICEP) Northwestern University 2145 Sheridan Road Evanston IL 60208-3113 USA

Abstract

Polyethylene terephthalate (PET) is selectively depolymerized by a carbon‐supported single‐site molybdenum‐dioxo catalyst to terephthalic acid (PTA) and ethylene. The solventless reactions are most efficient under 1 atmosphere of H ₂ . The catalyst exhibits high stability and can be recycled multiple times without loss of activity. Waste beverage bottle PET or a PET + polypropylene (PP) mixture (simulating the bottle + cap) proceeds at 260 °C with complete PET deconstruction and quantitative PTA isolation. Mechanistic studies with a model diester, 1,2‐ethanediol dibenzoate, suggest the reaction proceeds by initial retro‐hydroalkoxylation/β‐C−O scission and subsequent hydrogenolysis of the vinyl benzoate intermediate.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-03ER15457

OSTI ID:: 1668096

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 45 Vol. 132; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (63)

Der Abbau von Polyäthylenterephthalat Buxbaum, L. H. Angewandte Chemie, Vol. 80, Issue 6 https://doi.org/10.1002/ange.19680800604	journal	March 1968
Efficient Homogeneous Catalytic Hydrogenation of Esters to Alcohols Zhang, Jing; Leitus, Gregory; Ben-David, Yehoshoa Angewandte Chemie, Vol. 118, Issue 7 https://doi.org/10.1002/ange.200503771	journal	February 2006
The Degradation of Poly(ethylene terephthalate) Buxbaum, L. H. Angewandte Chemie International Edition in English, Vol. 7, Issue 3 https://doi.org/10.1002/anie.196801821	journal	March 1968
Efficient Homogeneous Catalytic Hydrogenation of Esters to Alcohols Zhang, Jing; Leitus, Gregory; Ben-David, Yehoshoa Angewandte Chemie International Edition, Vol. 45, Issue 7 https://doi.org/10.1002/anie.200503771	journal	February 2006
A novel catalyst for the glycolysis of poly(ethylene terephthalate) Troev, K.; Grancharov, G.; Tsevi, R. Journal of Applied Polymer Science, Vol. 90, Issue 8 https://doi.org/10.1002/app.12711	journal	January 2003
Glycolysis of postconsumer polyethylene terephthalate waste Pingale, Navnath D.; Palekar, Vikrant S.; Shukla, S. R. Journal of Applied Polymer Science, Vol. 115, Issue 1 https://doi.org/10.1002/app.31092	journal	January 2010
Efficient Chemoselective Reduction of N ‐Oxides and Sulfoxides Using a Carbon‐Supported Molybdenum‐Dioxo Catalyst and Alcohol Li, Jiaqi; Liu, Shengsi; Lohr, Tracy L. ChemCatChem, Vol. 11, Issue 16 https://doi.org/10.1002/cctc.201900436	journal	May 2019
On the Functional Group Tolerance of Ester Hydrogenation and Polyester Depolymerisation Catalysed by Ruthenium Complexes of Tridentate Aminophosphine Ligands Fuentes, José A.; Smith, Samuel M.; Scharbert, M. Theresa Chemistry - A European Journal, Vol. 21, Issue 30 https://doi.org/10.1002/chem.201500907	journal	June 2015
Recycling of Polymers: A Review Ignatyev, Igor A.; Thielemans, Wim; Vander Beke, Bob ChemSusChem, Vol. 7, Issue 6 https://doi.org/10.1002/cssc.201300898	journal	May 2014
Room Temperature Organocatalyzed Reductive Depolymerization of Waste Polyethers, Polyesters, and Polycarbonates Feghali, Elias; Cantat, Thibault ChemSusChem, Vol. 8, Issue 6 https://doi.org/10.1002/cssc.201500054	journal	February 2015
Solubilization and Upgrading of High Polyethylene Terephthalate Loadings in a Low-Costing Bifunctional Ionic Liquid Sun, Jian; Liu, Dajiang; Young, Robert P. ChemSusChem, Vol. 11, Issue 4 https://doi.org/10.1002/cssc.201701798	journal	January 2018
A review on thermal decomposition and combustion of thermoplastic polyesters Levchik, Sergei V.; Weil, Edward D. Polymers for Advanced Technologies, Vol. 15, Issue 12 https://doi.org/10.1002/pat.526	journal	December 2004
Enzyme-catalyzed transesterification of vinyl esters on cellulose solids Xie, Jiangbing; Hsieh, You-Lo Journal of Polymer Science Part A: Polymer Chemistry, Vol. 39, Issue 11 https://doi.org/10.1002/pola.1170	journal	January 2001
Unexpected efficiency of cyclic amidine catalysts in depolymerizing poly(ethylene terephthalate) Fukushima, Kazuki; Coady, Daniel J.; Jones, Gavin O. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 51, Issue 7 https://doi.org/10.1002/pola.26530	journal	January 2013
Thermal degradation studies of terephthalate polyesters: 1. Poly(alkylene terephthalates) McNeill, I. C.; Bounekhel, M. Polymer Degradation and Stability, Vol. 34, Issue 1-3 https://doi.org/10.1016/0141-3910(91)90119-C	journal	January 1991
Studies on thermal and thermo-oxidative degradation of poly(ethylene terephthalate) and poly(butylene terephthalate) Botelho, Gabriela; Queirós, Arlete; Liberal, Sofia Polymer Degradation and Stability, Vol. 74, Issue 1 https://doi.org/10.1016/S0141-3910(01)00088-X	journal	January 2001
Thermal degradation of poly(ethylene terephthalate) at the processing temperature Samperi, Filippo; Puglisi, Concetto; Alicata, Rossana Polymer Degradation and Stability, Vol. 83, Issue 1 https://doi.org/10.1016/S0141-3910(03)00166-6	journal	January 2004
Fe-containing magnetic ionic liquid as an effective catalyst for the glycolysis of poly(ethylene terephthalate) Wang, Hui; Yan, Ruiyi; Li, Zengxi Catalysis Communications, Vol. 11, Issue 8 https://doi.org/10.1016/j.catcom.2010.02.011	journal	March 2010
Catalytic pyrolysis of polystyrene and polyethylene terephthalate over Al-MSU-F Oh, Daejun; Lee, Hyung Won; Kim, Young-Min Energy Procedia, Vol. 144 https://doi.org/10.1016/j.egypro.2018.06.015	journal	July 2018
Benzoic acid recovery via waste poly(ethylene terephthalate) (PET) catalytic pyrolysis using sulphated zirconia catalyst Diaz-Silvarrey, Laura S.; McMahon, Andrew; Phan, Anh N. Journal of Analytical and Applied Pyrolysis, Vol. 134 https://doi.org/10.1016/j.jaap.2018.08.014	journal	September 2018
Ethylene addition to group-6 transition metal oxo complexes – A theoretical study Haunschild, Robin; Frenking, Gernot Journal of Organometallic Chemistry, Vol. 693, Issue 4 https://doi.org/10.1016/j.jorganchem.2007.12.008	journal	February 2008
Combining Reclaimed PET with Bio-based Monomers Enables Plastics Upcycling Rorrer, Nicholas A.; Nicholson, Scott; Carpenter, Alberta Joule, Vol. 3, Issue 4 https://doi.org/10.1016/j.joule.2019.01.018	journal	April 2019
Manganese-, cobalt-, and zinc-based mixed-oxide spinels as novel catalysts for the chemical recycling of poly(ethylene terephthalate) via glycolysis Imran, Muhammad; Kim, Do Hyun; Al-Masry, Waheed A. Polymer Degradation and Stability, Vol. 98, Issue 4 https://doi.org/10.1016/j.polymdegradstab.2013.01.007	journal	April 2013
Reactivity of a Carbon-Supported Single-Site Molybdenum Dioxo Catalyst for Biodiesel Synthesis Mouat, Aidan R.; Lohr, Tracy L.; Wegener, Evan C. ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b01717	journal	September 2016
Conversion of Polyethylene Terephthalate Based Waste Carpet to Benzene-Rich Oils through Thermal, Catalytic, and Catalytic Steam Pyrolysis Du, Shoucheng; Valla, Julia A.; Parnas, Richard S. ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 5 https://doi.org/10.1021/acssuschemeng.6b00450	journal	April 2016
Depolymerization of Waste Plastics to Monomers and Chemicals Using a Hydrosilylation Strategy Facilitated by Brookhart’s Iridium(III) Catalyst Monsigny, Louis; Berthet, Jean-Claude; Cantat, Thibault ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 8 https://doi.org/10.1021/acssuschemeng.8b01842	journal	June 2018
Ultrasmall Cobalt Nanoparticles as a Catalyst for PET Glycolysis: A Green Protocol for Pure Hydroxyethyl Terephthalate Precipitation without Water Veregue, Fernanda Reis; Pereira da Silva, Cleiser Thiago; Moisés, Murilo Pereira ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 9 https://doi.org/10.1021/acssuschemeng.8b02294	journal	July 2018
The Depolymerization of Poly(ethylene terephthalate) (PET) Using N-Heterocyclic Carbenes from Ionic Liquids Kamber, Nahrain E.; Tsujii, Yasuhito; Keets, Kate Journal of Chemical Education, Vol. 87, Issue 5 https://doi.org/10.1021/ed800152c	journal	May 2010
Recent Developments in the Chemical Recycling of Postconsumer Poly(ethylene terephthalate) Waste George, Neena; Kurian, Thomas Industrial & Engineering Chemistry Research, Vol. 53, Issue 37 https://doi.org/10.1021/ie501995m	journal	September 2014
Chemical Recycling of Poly(ethylene terephthalate) Paszun, Daniel; Spychaj, Tadeusz Industrial & Engineering Chemistry Research, Vol. 36, Issue 4 https://doi.org/10.1021/ie960563c	journal	April 1997
Multiphoton Infrared Initiated Thermal Reactions of Esters: Pseudopericyclic Eight-Centered cis -Elimination Ji, Hua; Li, Li; Xu, Xiaolian Journal of the American Chemical Society, Vol. 131, Issue 2 https://doi.org/10.1021/ja804812c	journal	January 2009
Tris(pentafluorophenyl)boron-Catalyzed Hydrosilation of Aromatic Aldehydes, Ketones, and Esters Parks, Daniel J.; Piers, Warren E. Journal of the American Chemical Society, Vol. 118, Issue 39 https://doi.org/10.1021/ja961536g	journal	January 1996
Proton-Coupled Electron Transfer to a Molybdenum Ethylene Complex Yields a β-Agostic Ethyl: Structure, Dynamics and Mechanism Bezdek, Máté J.; Chirik, Paul J. Journal of the American Chemical Society, Vol. 140, Issue 42 https://doi.org/10.1021/jacs.8b08460	journal	September 2018
Kinetic Isotope Effects as a Guide to Transition State Geometries for the Intramolecular Cope and Ylide Elimination Reactions. An ab Initio MO Study Bach, Robert D.; Gonzalez, Carlos; Andres, Jose L. The Journal of Organic Chemistry, Vol. 60, Issue 14 https://doi.org/10.1021/jo00119a053	journal	July 1995
Mechanisms of Organocatalytic Amidation and Trans-Esterification of Aromatic Esters As a Model for the Depolymerization of Poly(ethylene) Terephthalate Horn, Hans W.; Jones, Gavin O.; Wei, DiDi S. The Journal of Physical Chemistry A, Vol. 116, Issue 51 https://doi.org/10.1021/jp304212y	journal	December 2012
Hydrolysis of Alkenyl Esters and Ethers Catalyzed by Metal Complexes Aoyama, Hiroshi; Tokunaga, Makoto; Hiraiwa, Shin-ichiro Organic Letters, Vol. 6, Issue 4 https://doi.org/10.1021/ol036228j	journal	February 2004
Some Organometallic Chemistry of Molybdenum Complexes that Contain the [HIPTN ₃ N] ³ ^- Triamidoamine Ligand, {[3,5-(2,4,6- i -Pr ₃ C ₆ H ₂ ) ₂ C ₆ H ₃ NCH ₂ CH ₂ ] ₃ N} ³ ^- Byrnes, Matthew J.; Dai, Xuliang; Schrock, Richard R. Organometallics, Vol. 24, Issue 18 https://doi.org/10.1021/om050373e	journal	August 2005
β-Heteroatom versus β-Hydrogen Elimination: A Theoretical Study Zhao, Haitao; Ariafard, Alireza; Lin, Zhenyang Organometallics, Vol. 25, Issue 4 https://doi.org/10.1021/om050703v	journal	February 2006
Reactions of mer -Mo(H)(CO)(NO)(PMePh ₂ ) ₃ with Ethylene, Propylene, and Styrene That Bear on Alternating CO/Olefin Coupling Chemistry Cheng, Tan-Yun; Southern, Joel S.; Hillhouse, Gregory L. Organometallics, Vol. 16, Issue 11 https://doi.org/10.1021/om970160s	journal	May 1997
First-Row Transition Metal-Containing Ionic Liquids as Highly Active Catalysts for the Glycolysis of Poly(ethylene terephthalate) (PET) Wang, Qian; Geng, Yanrong; Lu, Xingmei ACS Sustainable Chemistry & Engineering, Vol. 3, Issue 2 https://doi.org/10.1021/sc5007522	journal	January 2015
Chemical recycling of waste plastics for new materials production Rahimi, AliReza; García, Jeannette M. Nature Reviews Chemistry, Vol. 1, Issue 6 https://doi.org/10.1038/s41570-017-0046	journal	June 2017
An engineered PET depolymerase to break down and recycle plastic bottles Tournier, V.; Topham, C. M.; Gilles, A. Nature, Vol. 580, Issue 7802 https://doi.org/10.1038/s41586-020-2149-4	journal	April 2020
Mechanistic comparison of β-H elimination, β-OH elimination, and nucleophilic displacement reactions of β-hydroxy alkyl rhodium porphyrin complexes Wu, Bing; Zhang, Jiadi; Yun, Lin Dalton Trans., Vol. 40, Issue 10 https://doi.org/10.1039/C0DT01146K	journal	January 2011
Superparamagnetic γ-Fe ₂ O ₃ nanoparticles as an easily recoverable catalyst for the chemical recycling of PET Bartolome, Leian; Imran, Muhammad; Lee, Kyoung G. Green Chem., Vol. 16, Issue 1 https://doi.org/10.1039/C3GC41834K	journal	January 2014
Efficient catalytic greenhouse gas-free hydrogen and aldehyde formation from aqueous alcohol solutions Lohr, Tracy L.; Mouat, Aidan R.; Schweitzer, Neil M. Energy & Environmental Science, Vol. 10, Issue 7 https://doi.org/10.1039/C6EE03739A	journal	January 2017
Fe ₃ O ₄ -boosted MWCNT as an efficient sustainable catalyst for PET glycolysis Al-Sabagh, A. M.; Yehia, F. Z.; Harding, David R. K. Green Chemistry, Vol. 18, Issue 14 https://doi.org/10.1039/C6GC00534A	journal	January 2016
Efficient carbon-supported heterogeneous molybdenum-dioxo catalyst for chemoselective reductive carbonyl coupling Liu, Shengsi; Li, Jiaqi; Jurca, Titel Catalysis Science & Technology, Vol. 7, Issue 11 https://doi.org/10.1039/C7CY00336F	journal	January 2017
Chemically recyclable polymers: a circular economy approach to sustainability Hong, Miao; Chen, Eugene Y. -X. Green Chemistry, Vol. 19, Issue 16 https://doi.org/10.1039/C7GC01496A	journal	January 2017
Comparing conventional and microwave-assisted heating in PET degradation mediated by imidazolium-based halometallate complexes Scé, Fabio; Cano, Israel; Martin, Carmen New Journal of Chemistry, Vol. 43, Issue 8 https://doi.org/10.1039/C8NJ06090H	journal	January 2019
Dioxomolybdenum complex as an efficient and cheap catalyst for the reductive depolymerization of plastic waste into value-added compounds and fuels Nunes, Beatriz F. S.; Oliveira, M. Conceição; Fernandes, Ana C. Green Chemistry, Vol. 22, Issue 8 https://doi.org/10.1039/C9GC04206G	journal	January 2020
Selective C–O bond cleavage of allylic esters using [MoH ₄ (Ph ₂ PCH ₂ CH ₂ PPh ₂ ) ₂ ] under light irradiation to give hydridocarboxylatomolybdenum( II ) complexes Ito, Takashi; Matsubara, Tetsuaki; Yamashita, Yoichiro J. Chem. Soc., Dalton Trans., Issue 8 https://doi.org/10.1039/DT9900002407	journal	January 1990
Urea as an efficient and reusable catalyst for the glycolysis of poly(ethylene terephthalate) wastes and the role of hydrogen bond in this process Wang, Qian; Yao, Xiaoqian; Tang, Shaofeng Green Chemistry, Vol. 14, Issue 9 https://doi.org/10.1039/c2gc35696a	journal	January 2012
One-step sonochemical synthesis of a graphene oxide–manganese oxide nanocomposite for catalytic glycolysis of poly(ethylene terephthalate) Park, Gle; Bartolome, Leian; Lee, Kyoung G. Nanoscale, Vol. 4, Issue 13 https://doi.org/10.1039/c2nr30168g	journal	January 2012
Controlled hydrogenative depolymerization of polyesters and polycarbonates catalyzed by ruthenium(ii) PNN pincer complexes Krall, Eric M.; Klein, Tyler W.; Andersen, Ryan J. Chemical Communications, Vol. 50, Issue 38 https://doi.org/10.1039/c4cc00541d	journal	January 2014
The kinetic isotope effect in the pyrolysis of esters and the nature of the transition state Taylor, R. Journal of the Chemical Society, Perkin Transactions 2, Issue 2 https://doi.org/10.1039/p29720000165	journal	January 1972
News Feature: On the brink of a recycling revolution? Carey, John Proceedings of the National Academy of Sciences, Vol. 114, Issue 4 https://doi.org/10.1073/pnas.1620655114	journal	January 2017
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
Molecular catalyst systems as key enablers for tailored polyesters and polycarbonate recycling concepts Westhues, Stefan; Idel, Jasmine; Klankermayer, Jürgen Science Advances, Vol. 4, Issue 8 https://doi.org/10.1126/sciadv.aat9669	journal	August 2018
Plastic waste inputs from land into the ocean Jambeck, J. R.; Geyer, R.; Wilcox, C. Science, Vol. 347, Issue 6223 https://doi.org/10.1126/science.1260352	journal	February 2015
A bacterium that degrades and assimilates poly(ethylene terephthalate) Yoshida, Shosuke; Hiraga, Kazumi; Takehana, Toshihiko Science, Vol. 351, Issue 6278 https://doi.org/10.1126/science.aad6359	journal	March 2016
Plastics recycling with a difference Sardon, Haritz; Dove, Andrew P. Science, Vol. 360, Issue 6387 https://doi.org/10.1126/science.aat4997	journal	April 2018
Melting Behavior of Poly(ethylene terephthalate) Crystallized and Annealed under Elevated Pressure Hiramatsu, Nobuyasu; Hirakawa, Susumu Polymer Journal, Vol. 12, Issue 2 https://doi.org/10.1295/polymj.12.105	journal	February 1980
Poly(1,4-cyclohexanedimethylene 2,6-naphthalate) polyester with high melting point: Effect of different synthesis methods on molecular weight and properties Kasmi, N.; Terzopoulou, Z.; Papageorgiou, G. Z. Express Polymer Letters, Vol. 12, Issue 3 https://doi.org/10.3144/expresspolymlett.2018.21	journal	January 2018

Similar Records

Polyethylene Terephthalate Deconstruction Catalyzed by a Carbon–Supported Single–Site Molybdenum–Dioxo Complex

Journal Article · Fri Jul 24 00:00:00 EDT 2020 · Angewandte Chemie (International Edition) · OSTI ID:2480919

Polyethylene Terephthalate Deconstruction Catalyzed by a Carbon‐Supported Single‐Site Molybdenum‐Dioxo Complex

Citation Formats

References (63)

Similar Records

Related Subjects