Depolymerization of polyesters by a binuclear catalyst for plastic recycling

Zhang, Shengbo; Hu, Qikun; Zhang, Yu-Xiao; Guo, Haoyue; Wu, Yanfen; Sun, Mingze; Zhu, Xingsong; Zhang, Jiangang; Gong, Shuyan; Liu, Ping; Niu, Zhiqiang

doi:10.1038/s41893-023-01118-4

Depolymerization of polyesters by a binuclear catalyst for plastic recycling

Journal Article · Mon May 01 00:00:00 EDT 2023 · Nature Sustainability

DOI:https://doi.org/10.1038/s41893-023-01118-4· OSTI ID:1986317

Zhang, Shengbo ^[1]; ^[1]; ^[1]; Guo, Haoyue ^[2]; Wu, Yanfen ^[1]; ^[1]; Zhu, Xingsong ^[3]; ^[1]; Gong, Shuyan ^[1]; ^[2]; ^[1]

Tsinghua Univ., Beijing (China)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sinopec Yizheng Chemical Fibre Co., Ltd., Yangzhou (China)

Plastics play an essential role in modern society, however, the relentless growth of their production is threatening both human health and ecosystems. As a result, there are intensive efforts in developing recycling technologies to repurpose waste plastics into the building blocks for valuable materials. Here we show a binuclear complex that can catalyze the degradation of polyethylene terephthalate (PET)-the most widely used polyester globally-and a wide spectrum of other plastics including polylactic acid (PLA), polybutylene adipate terephthalate (PBAT), polycaprolactone (PCL), polyurethane (PU) and Nylon 66. Inspired by hydrolases, the group of enzymes that catalyze bond cleavages with water, the present catalyst design features biomimetic Zn-Zn sites which activate the plastic, stabilize the key intermediate, and enable intramolecular hydrolysis. This synthetic catalyst delivers activities of 36 mg_PET d^-1 g_catal^-1 toward PET depolymerization at pH 8 and 40 oC, and of 577 g_PET d^-1 g_catal^-1 at pH 13 and 90 oC for scalable PET recycling. We further demonstrate the closed-loop production of a bottle-grade PET. This work presents a practical and viable solution to the sustainable management of plastics waste.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: China Postdoctoral Science Foundation; National Key R&D Program of China; National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1986317

Report Number(s):: BNL--224510-2023-JAAM

Journal Information:: Nature Sustainability, Journal Name: Nature Sustainability Vol. 6; ISSN 2398-9629

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Highly Efficient Solid‐State Hydrolysis of Waste Polyethylene Terephthalate by Mechanochemical Milling and Vapor‐Assisted Aging Štrukil, Vjekoslav ChemSusChem, Vol. 14, Issue 1 https://doi.org/10.1002/cssc.202002124	journal	October 2020
Current knowledge on enzymatic PET degradation and its possible application to waste stream management and other fields Kawai, Fusako; Kawabata, Takeshi; Oda, Masayuki Applied Microbiology and Biotechnology, Vol. 103, Issue 11 https://doi.org/10.1007/s00253-019-09717-y	journal	April 2019
An FT–IR study of the effect of hydrolytic degradation on the structure of thin PET films Sammon, Chris; Yarwood, Jack; Everall, Neil Polymer Degradation and Stability, Vol. 67, Issue 1 https://doi.org/10.1016/S0141-3910(99)00104-4	journal	January 2000
Effect of hydrolysis products on the enzymatic degradation of polyethylene terephthalate nanoparticles by a polyester hydrolase from Thermobifida fusca Barth, Markus; Oeser, Thorsten; Wei, Ren Biochemical Engineering Journal, Vol. 93 https://doi.org/10.1016/j.bej.2014.10.012	journal	January 2015
Recent advances in biocatalysts engineering for polyethylene terephthalate plastic waste green recycling Samak, Nadia A.; Jia, Yunpu; Sharshar, Moustafa M. Environment International, Vol. 145 https://doi.org/10.1016/j.envint.2020.106144	journal	December 2020
Charge-separated metal-couple-site in NiZn alloy catalysts towards furfural hydrodeoxygenation reaction Meng, Xiaoyu; Wang, Lei; Chen, Lifang Journal of Catalysis, Vol. 392 https://doi.org/10.1016/j.jcat.2020.10.003	journal	December 2020
Zinc-catalyzed ester bond cleavage: Chemical degradation of polyethylene terephthalate Wang, Yuqi; Zhang, Yao; Song, Hongyan Journal of Cleaner Production, Vol. 208 https://doi.org/10.1016/j.jclepro.2018.10.117	journal	January 2019
Techno-economic, life-cycle, and socioeconomic impact analysis of enzymatic recycling of poly(ethylene terephthalate) Singh, Avantika; Rorrer, Nicholas A.; Nicholson, Scott R. Joule, Vol. 5, Issue 9 https://doi.org/10.1016/j.joule.2021.06.015	journal	September 2021
Enzyme discovery and engineering for sustainable plastic recycling Zhu, Baotong; Wang, Dong; Wei, Na Trends in Biotechnology, Vol. 40, Issue 1 https://doi.org/10.1016/j.tibtech.2021.02.008	journal	January 2022
Artificial Metalloenzymes: Reaction Scope and Optimization Strategies Schwizer, Fabian; Okamoto, Yasunori; Heinisch, Tillmann Chemical Reviews, Vol. 118, Issue 1 https://doi.org/10.1021/acs.chemrev.7b00014	journal	May 2017
Reaction Mechanism of MHETase, a PET Degrading Enzyme Pinto, Alexandre V.; Ferreira, Pedro; Neves, Rui P. P. ACS Catalysis, Vol. 11, Issue 16 https://doi.org/10.1021/acscatal.1c02444	journal	August 2021
Binuclear Metallohydrolases: Complex Mechanistic Strategies for a Simple Chemical Reaction Schenk, Gerhard; Mitić, Nataša; Gahan, Lawrence R. Accounts of Chemical Research, Vol. 45, Issue 9 https://doi.org/10.1021/ar300067g	journal	June 2012
The Catalytic Mechanisms of Binuclear Metallohydrolases Mitić, Nataša; Smith, Sarah J.; Neves, Ademir Chemical Reviews, Vol. 106, Issue 8 https://doi.org/10.1021/cr050318f	journal	August 2006
Binuclear Metallohydrolases Wilcox, Dean E. Chemical Reviews, Vol. 96, Issue 7 https://doi.org/10.1021/cr950043b	journal	January 1996
Dinuclear Zinc(II) Complexes of Tetraiminodiphenol Macrocycles and Their Interactions with Carboxylate Anions and Amino Acids. Photoluminescence, Equilibria, and Structure Dutta, Bula; Bag, Pradip; Flörke, Ulrich Inorganic Chemistry, Vol. 44, Issue 1 https://doi.org/10.1021/ic049056a	journal	November 2004
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
Substrate-Promoted Formation of a Catalytically Competent Binuclear Center and Regulation of Reactivity in a Glycerophosphodiesterase from Enterobacter aerogenes Hadler, Kieran S.; Tanifum, Eric A.; Yip, Sylvia Hsu-Chen Journal of the American Chemical Society, Vol. 130, Issue 43 https://doi.org/10.1021/ja803346w	journal	October 2008
Hydrolysis of polyesters by lipases Tokiwa, Yutaka; Suzuki, Tomoo Nature, Vol. 270, Issue 5632 https://doi.org/10.1038/270076a0	journal	November 1977
Classify plastic waste as hazardous Rochman, Chelsea M.; Browne, Mark Anthony; Halpern, Benjamin S. Nature, Vol. 494, Issue 7436 https://doi.org/10.1038/494169a	journal	February 2013
Interaction between liquid water and hydroxide revealed by core-hole de-excitation Aziz, Emad F.; Ottosson, Niklas; Faubel, Manfred Nature, Vol. 455, Issue 7209 https://doi.org/10.1038/nature07252	journal	September 2008
Structural insight into catalytic mechanism of PET hydrolase Han, Xu; Liu, Weidong; Huang, Jian-Wen Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-02255-z	journal	December 2017
Structural insight into molecular mechanism of poly(ethylene terephthalate) degradation Joo, Seongjoon; Cho, In Jin; Seo, Hogyun Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-02881-1	journal	January 2018
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
Near-complete depolymerization of polyesters with nano-dispersed enzymes DelRe, Christopher; Jiang, Yufeng; Kang, Philjun Nature, Vol. 592, Issue 7855 https://doi.org/10.1038/s41586-021-03408-3	journal	April 2021
Recovering waste plastics using shape-selective nano-scale reactors as catalysts Zhang, Zheng; Gora-Marek, Kinga; Watson, Jonathan S. Nature Sustainability, Vol. 2, Issue 1 https://doi.org/10.1038/s41893-018-0195-9	journal	January 2019
Detailing plastic pollution Guha Roy, Aimee Nature Sustainability, Vol. 2, Issue 8 https://doi.org/10.1038/s41893-019-0367-2	journal	August 2019
General features to enhance enzymatic activity of poly(ethylene terephthalate) hydrolysis Chen, Chun-Chi; Han, Xu; Li, Xian Nature Catalysis, Vol. 4, Issue 5 https://doi.org/10.1038/s41929-021-00616-y	journal	May 2021
Chemical and biological catalysis for plastics recycling and upcycling Ellis, Lucas D.; Rorrer, Nicholas A.; Sullivan, Kevin P. Nature Catalysis, Vol. 4, Issue 7 https://doi.org/10.1038/s41929-021-00648-4	journal	July 2021
Characterization and engineering of a plastic-degrading aromatic polyesterase Austin, Harry P.; Allen, Mark D.; Donohoe, Bryon S. Proceedings of the National Academy of Sciences, Vol. 115, Issue 19 https://doi.org/10.1073/pnas.1718804115	journal	April 2018
Enzymatic depolymerization of highly crystalline polyethylene terephthalate enabled in moist-solid reaction mixtures Kaabel, Sandra; Therien, J. P. Daniel; Deschênes, Catherine E. Proceedings of the National Academy of Sciences, Vol. 118, Issue 29 https://doi.org/10.1073/pnas.2026452118	journal	July 2021
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
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
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
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
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
Spectroscopic snapshots of the proton-transfer mechanism in water Wolke, C. T.; Fournier, J. A.; Dzugan, L. C. Science, Vol. 354, Issue 6316 https://doi.org/10.1126/science.aaf8425	journal	December 2016
The global threat from plastic pollution MacLeod, Matthew; Arp, Hans Peter H.; Tekman, Mine B. Science, Vol. 373, Issue 6550 https://doi.org/10.1126/science.abg5433	journal	July 2021

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Depolymerization of polyesters by a binuclear catalyst for plastic recycling

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