4619/28, 1058 PM Miccowave-assisted depolymerization of PET over heterogeneous catalysis - ScienceDirect ae ScienceDirect” Catalysis Today Volume 418, 1 June 2023, 114124 Microwave-assisted depolymerization of PET over heterogeneous catalysts Esun Selvam®, Yuqing Luo *, Marianthi lerapetritou® 9, pg, Raul. Lobo*? 9, 73, Dionisios G,Vlachos*® 2 ey Show more v Share 59 Cite httpd. org/20.1016)j Get rights and content » Abstract ‘The accumulation of plastic waste in the environment is rising and poses a significant environmental and health threat. Polyethylene terephthalate (PET), used mainly in single-use plastic bottles, accounts for a substantial fraction of this waste. The currently employed recycling strategies are inadequate to deal with the global plastic waste problem. PET glycolysis is a promising depolymerization method but has mainly been conducted using homogeneous catalysts; developing active and sustainable catalysts, and more energy-efficient processes remain challenges. Here, we implement microwave heating in PET glycolysis and identify ZnO as an excellent heterogeneous catalyst. We demonstrate the influence of Zn0's particle size and facet and hydrogen bonding on its activity. Finally, we demonstrate excellent performance for real-world post-consumer PET waste deconstruction with rapid depolymerization into bis(2-hydroxyethyl) terephthalate (BHET), achieving >95% yields in less than 10min. Cradle-to-gate life cycle assessment also indicates that BHET produced by ZnO-catalyzed glycolysis has lower global warming potential than the petrochemical-based production and homogeneously-catalyzed glycolysis. Graphical Abstract hitpssiwwwscioncedie ‘comisciencelarticelabsipivS0920586123001487 wr4619/28, 1058 PM Miccowave-assisted depolymerization of PET over heterogeneous catalysis - ScenceDirect act Download : Download high-res image (82KB) Download : Download fullsize image Introduction Plastics have become an integral part of countless consumer and industrial applications dute to their high versatility, low cost, and easily tunable application-specific properties [1]. As a result, the global production of plastics has been rising, with polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), and polyvinyl chloride (PVC) accounting for most of the plastics [2]. With the current production and waste ‘management strategy, ~12 billion tons of plastics will be accumulated in landfills or the environment by 2050, and the oceans could contain more plastics than fish [3]. Although incineration eliminates unwanted plastics andl recovers energy, it creates unwanted byproducts with profound environmental impact. Mechanical recycling degrades or downcycles polymers and is tnststainable [4]. Chemical conversion of the polymers to monomers (recycling) or value-added products (upeycling), such as fuels, chemicals, lubricants, etc, can enable a circular and sustainable economy (2], [5]. PET is a semi-crystalline thermoplastic polyester resin of terephthalic acid (TPA) and ethylene glycol (EG). It is highly versatile with excellent thermal and mechanical stability, low water absorption, good gas barrier properties, and good chemical resistance. These properties make it suitable for applications such as carpeting, polyester textile manufacturing, and mainly for storing food and liquids in single-use beverage bottles and plastic packages [6]. PET's production was ~50 million tons in 2016 and is expected to be ~87 million tons by 2022; [7] ~1 million plastic drinking bottles are purchased every minute! [8] Its increasing consumption and non-biodegradability [9] (natural decomposition takes over 450 years) make it a severe environmental, social, and economic concern. At present, <20% of the PET waste is mechanically recycled [10]. As alluded above, this leads to quality downgrade (thermal degradation, defilement, discoloration) [11] making the recycled material only suitable for low-grade applications and eventually landfills. ‘The chemical recycling of PET is very actively studied, with solvolysis being the most viable method [12]. Glycolysis, the depolymerization in EG solvent, in particular, is an excellent technology due to fast depolymerization stemming from the strong nucleophilicity of EG and easy separability of the monomer, bis(2-hydroxyethyl) terephthalate (BHET) [6], [11], [12]. BHET, the esterification product of TPA with EG, can be recycled directly, eliminating the extra esterification step [6]. Most PET glycolysis studies have employed homogeneous catalysts, such as acetate, chloride, and carbonate salts of transition metals, including Zn, Pb, Mn, Co, Fe, and other amine-based organometallics, which are active but have poor reusability and impose hitpssiwwwscioncedie ‘comisciencelarticelabsipivS0920586123001487879723, 1058 PM Microwave-assisted depolymerization of PET over heterogeneous catalysis - ScienceDirect environmental concerns [11], [12], [13], [14] as they are often hard to separate and recycle. They may end up in the polymer affecting end-product quality, Sustainable, inexpensive, and abundant heterogeneous catalysts and ionic liquids (ILs) could transform commercialization and sustainability (15), [16], [17], [18] However, heterogeneous catalysts typically possess relatively low activity (Fig. $1). More recently, there has been interest in studying metal oxides of transition metals such as Zn, Ti, Co, etc. as sustainable alternatives for homogeneous catalysts.[15}, [16], [19] ZnO has been one such oxide that has shown promise; however, the monomer yields have been modest (<85%) and processing times have been long (1~4h), even with PET bottle waste which is easier to depolymerize (Fig. 1). Aside from the lack of active heterogeneous catalysts, the heating of plastics is another major challenge due to their very low thermal conductivity. This, in turn, results in large and high capital cost reactors, rendering distributed recycling hard and energy efficiency low. Developing sustainable catalysts and processes is thus essential. In the last decade, microwaves have been used extensively due to their rapid and selective heating. Under microwave irradiation, the dipoles of polar molecules rotate as they align with the alternating electromagnetic field (2450 million times per second) [20]. generating friction and dissipating energy as heat, a phenomenon known as dipolar polarization [20]. A material's ability to convert electromagnetic energy into heat (at a given frequency and temperature) is determined by its dielectric loss tangent (tané = e"Je') [20], [21]. The high tan6 of EG (Table $1) makes it an excellent solvent for microwave heating (Fig. $2). In conjunction with its high nucleophilicity, EG is an ideal solvent for microwave-assisted glycolysis. Here, we investigate Zn-based solid materials as potential catalysts and identify zinc oxide (ZnO) as an active catalyst for the microwave-assisted glycolysis of PET. We engineer ZnO performance via facet and size control. We demonstrate that microwave reactors are excellent for rapid heating and recycling and compare their performance with conventional glycolysis. Furthermore, we show that the catalysts are reusable and can be applied to real-life plastics with > 95% molar yields of the monomer. Life cycle assessment (LCA) for the heterogeneously-catalyzed PET glycolysis shows that the greenhouse gas (GHG) emission is lower than the traditional process, using dimethyl terephthalate, and the homogeneously-catalyzed glycolysis reported in the literature. Section snippets Materials PET pellets (3-5 mm, Mw ~ 60 kDa) were obtained from Good Fellow Inc. Commercial PET beverage bottles ‘were washed with water, dried, and cut into small square pieces (~4 mm x 4mm). Commercial PET fibers and fabric samples were obtained from KECO and were cut into rectangular pieces (~16 mm x 9 mm). EG (anhydrous, 99.8%), BHET (> 98.4%), zinc oxide (<5 jim), zinc oxide (<100 nm), zinc oxide (<50 nm), zine sulphide (>99%), zinc selenide (>99%), zinc acetate dihydrate (>99.9%), zinc(II) chloride. Initial catalyst screening, selection and parameter optimization Our screening studies of homogeneous catalyst salts (Fig, $4), carried out at 210°C for 30 mins, and prior literature data underscore zinc salts as highly active for the glycolysis of PET [31], [32], [33]. We found that the typical Lewis acidic strength metric of the homogeneous catalysts does not correlate with the activity. hitpssiwwwscioncedie ‘comisciencelarticelabsipivS0920586123001487 a7879723, 1058 PM Microwave-assisted depolymerization of PET over heterogeneous catalysis - ScienceDirect Since Zn is highly active for the PET glycolysis, we chose ZnO as our initial material of choice for the further investigation of heterogeneous catalysts and process. Conclusions ‘We have successfully demonstrated that zine oxide (ZnO) catalysts are highly active and selective for the glycolysis of PET to produce bis(2-hydroxyethyl) terephthalate, achieving over 95% yields from virgin PET. Zn0's catalytic activity could be further enhanced by reducing its size and selectively increasing the exposure of polar facets. We hypothesized that the catalyst’s ability to form hydrogen bonds with EG can play a crucial role in determining its activity, even for heterogeneous. Funding ‘This work was supported as part of the Center for Plastics Innovation, an Energy Frontier Research Center, funded by the US. Dept. of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number DE-SC0021166. The microwave instrumentation was supported by the Department of Energy's Office of Energy Efficiencyand Renewable Energy's Advanced Manufacturing Office under Award Number DE- EE0007888-7.6 and the State of Delaware CRediT authorship contribution statement Esun Selvam: Conceptualization, Methodology, Investigation, Formal analysis, Writing ~ original draft, ‘Writing - review & editing. Yuqing Luo: Methodology, Formal analysis, Writing - original draft, Marianthi lerapetritou: Supervision, Writing - review & editing, Funding acquisition. Raul F. Lobo: Conceptualization, Supervision, Dionisios G. Vlachos: Conceptualization, Supervision, Writing - review & editing, Project administration, Funding acquisition... Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper... Acknowledgements This research used instruments in the Advanced Materials Characterization Lab (AMCL), W. M. Keck Center for Advanced Microscopy & Microanalysis, and the Mass Spectrometry Facility at the University of Delaware. ‘The authors used the NMR facilities at the University of Delaware, founded by the Delaware COBRE program, supported by a grant from the National Institute of General Medical Sciences - NIGMS (5 P30 GM110758-02) from the National Institutes of Health, The authors are grateful to Jeffery. References (55) P. Oblak et al. Processability and mechanical properties of extensively recycled high density polyethylene hitpssiwwwscioncedie ‘comisciencelarticelabsipivS0920586123001487 an879723, 1058 PM Microwave-assisted depolymerization of PET over heterogeneous catalysis - ScienceDirect Polym. Degrad. Stab. (2015) G. Xi etal. Study on depolymerization of waste polyethylene terephthalate into monomer of bis(2- hydroxyethyl terephthalate) Polym. Degrad. Stab. (2005) ‘M. Imran et al. Manganese-, cobalt-, and zinc-based mixed-oxide spinels as novel catalysts for the chemical recycling of poly(ethylene terephthalate) via glycolysis Polym. Degrad. Stab. (2013) JA. Menéndez etal Microwave heating processes involving carbon materials Fuel Process. Technol. (2010) X. Zhang et al. Gasoline-range hydrocarbons produced from microwave-induced pyrolysis of low-density polyethylene over ZSM-5 Fuel (2015) NA. Rorrer et al, Combining reclaimed PET with bio-based monomers enables plastics upcycling Joule (2019) R. Lépez+Fonseca et al. Chemical recycling of post-consumer PET wastes by glycolysis in the presence of metal salts Polym. Degrad. Stab. (2010) R. Lépex-Fonseca etal Kinetics of catalytic glycolysis of PET wastes with sodium carbonate Chem. Eng. J.(2011) Jel. Du etal. Zn0 nanodispersion as pseudohomogeneous catalyst for alcoholysis of polyethylene terephthalate Chem. Eng, Sci (2020) 1H. Zhang et al. Distinct water activation on polar/non-polar facets of ZnO nanoparticles J. Catal (2015) Y | View more references hitpssiwuw.sciencediract com/science/aricle‘abepivS0920586123001487‘1729, 1059 PM Mirowave-sssisted epolymerzaton of PET over heterogeneous catalysts - SicoOiect Cited by (0) Recommended articles (6) Research article Biphenyl dicarboxylates from ethene and bifuran dimethyl esters Molecular Catalysis, Volume 537, 2023, Article 112949 Show abstract Research article Sulfosuccinic acid-based metal-center catalysts for the synthesis of HMF from carbohydrates Catalysis Today, Volume 418, 2023, Article 114127 Show abstract Research article Computational screening of ys borophene based single-atom catalysts for Nz reduction Catalysis Today, Volume 418, 2023, Article 114079 Show abstract Research article Extraction of valuable chemicals from food waste via computational solvent screening and experiments Separation and Purification Technology, Volume 316, 2023, Article 123719 Show abstract Research article Single pot catalyst strategy to branched products via adhesive isomerization and hydrocracking of polyethylene over platinum tungstated zirconia ‘Applied Catalysis B: Environmental, Volume 299, 2021, Article 120483 Show abstract Research article Efficient glycolysis of recycling poly(ethylene terephthalate) via combination of organocatalyst and metal salt Polymer Degradation and Stability, Volume 206, 2022, Article 110168 Show abstract hitpssiwwwscioncedie ‘comisciencelarticelabsipivS09205861230014874619/28, 1058 PM Miccowave-assisted depolymerization of PET over heterogeneous catalysis - ScienceDirect View full text © 2023 Elsevier 8. Al rights reserved 2 conyiht © 202 ever, rs cerson or conv Ur SeereDireto sa repiterea temas of Hever BV tt SISRVTER hitpssiwuw.sciencediract com/science/aricle‘abepivS0920586123001487 @RELX" W